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Progress in Energy and Combustion Science 55 (2016) 98194

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Progress in Energy and Combustion Science


j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / p e c s

Ecient valorization of biomass to biofuels with bifunctional solid


catalytic materials
Hu Li a,b,d, Zhen Fang a,d,*, Richard L. Smith Jr. c, Song Yang b
a Biomass Group, College of Engineering, Nanjing Agricultural University, 40 Dianjiangtai Road, Nanjing, Jiangsu 210031, China
b State-Local Joint Engineering Laboratory for Comprehensive Utilization of Biomass, Center for R&D of Fine Chemicals, Guizhou University, Guiyang 550025, China
c
Research Center of Supercritical Fluid Technology, Graduate School of Environmental Studies, Tohoku University, Aramaki Aza Aoba 6-6-11, Aoba-ku, Sendai 980 8579, Japan
d
Chinese Academy of Sciences, Biomass Group, Key Laboratory of Tropical Plant Resources and Sustainable Use, Xishuangbanna Tropical Botanical Garden, 88 Xuefulu, Kunming,
Yunnan Province 650223, China

A R T I C L E I N F O A B S T R A C T

Article history: Mono-functional catalytic materials are used for many types of chemical transformations, but are tedious
Received 29 July 2015 for delivering products from multiple-step reactions required for the valorization of biomass. An emerg-
Accepted 20 April 2016 ing trend is to integrate catalytic transformations, reaction engineering and product separation into a
Available online 17 May 2016
single operation, wherein catalyst design is considered as the key approach to develop ecient, low energy
and environmentally-friendly reaction systems. Bifunctional solid catalysts open a door for carrying out
Keywords:
domino/cascade- and tandem/sequential-type reactions in a single pot, for which the number of isola-
Lignocellulose
tion or purication steps can be lessened or eliminated so that removal of unwanted by-products becomes
Catalyst design
Catalysis unnecessary. This review introduces bifunctional materials used in one-pot multiple transformations of
One-pot reaction biomass into biofuels and related chemicals. Emphasis is placed on the assessment of the bifunctionality
Platform chemicals of catalytic materials, including BronstedLewis acid, acidbase, and metal particlesacid or base bi-
Nanotechnology functional catalysts with some discussion being on combined catalytic systems with electrochemical, chemo-
enzymatic and photochemical methods. Plausible reaction mechanisms for key pathways are shown.
Relevant auxiliaries to boost catalytic activity and product selectivity, such as reaction media, heating
modes and morphological properties of the catalytic materials are analyzed. Use of appropriate bifunc-
tional catalytic materials provides many opportunities for design of highly ecient reaction systems and
simplied processing for producing biofuels and chemicals from lignocellulosic biomass.
2016 Elsevier Ltd. All rights reserved.

Abbreviations: AC, activated carbon; AgSTA, silver exchanged silicotungstic acid; APPO, aqueous phase partial oxidation; ATP, attapulgite; 1,4-BDO, 1,4-butanediol; BG,
1,4-butylene glycol; BHMF, 2,5-bis(hydroxymethyl)furan; BHMTF, 2,5-bis(hydroxymethyl)tetrahydrofuran; BMF, 5-bromomethylfurfural; [BMIM]Cl, 1-butyl-3-
methylimidazolium chloride; BS, benzene sulfonate; BV, BaeyerVilliger; CFP, catalytic fast pyrolysis; CMF, 5-chloromethylfurfural; CNFs, carbon nanobers; CNT, carbon
nanotube; Coni, -conidendrin; ConiA, -conidendric acid; CP, chloromethyl polystyrene; Cu-BTC, copper benzene-1,3,5-tricarboxylate; CVD, catalytic vapor deposition;
DBU, 1,8-diazabicyclo[5.4.0]undec-7-ene; DFF, 2,5-diformylfuran; DFT, density functional theory; DHA, dihydroxyacetone; DHH, 2,5-dihydroxyhexane; DMA,
N,N-dimethylacetamide; DMF, 2,5-dimethylfuran; DMSO, dimethylsulfoxide; DMTHF, 2,5-dimethyltetrahydrofuran; DS, dodecyl sulfate; DVB, divinylbenzene; EDX, energy-
dispersive X-ray spectroscopy; EG, ethylene glycol; EL, ethyl levulinate; EMF, 5-ethoxymethylfurfural; [EMIM]Cl, 1-ethyl-3-methylimidazolium chloride; F2Ac, 1,4-pentandien-
3-on-1,5-di-2-furanyl; FAc, 4-(2-furyl)-3-buten-2-on; FAMEs, fatty acid methyl esters; FDCA, 2,5-furandicarboxylic acid; FDMC, 2,5-dimethylfuroate; Fe3+-POP-1,
Fe3+-porous organic polymer; Fe-BTC, iron benzene-1,3,5-tricarboxylate; FfA, furfuryl alcohol; FFAs, free fatty acids; FFCA, 5-formyl-2-furancarboxylic acid; FT-IR, Fourier
transform infrared spectroscopy; GC-MS, gas chromatographymass spectrometry; GLY, glyceraldehyde; GO, graphene oxide; GVL, -valerolactone; HAA, hydroalkylation/
alkylation; HAP, hydroxylapatite; HDO, hydrodeoxygenation; HHD, 5-hydroxy-2,5-hexanedione; HMF, 5-hydroxymethylfurfural; HMFCA, 5-hydroxymethyl-2-
furancarboxylic acid; HMMF, 5-hydroxymethyl methylfuroate; HMR, hydroxymatairesinol; HNTs, halloysite nanotubes; HOAc, acetic acid; HPAs, heteropoly acids; HPLC, high-
performance liquid chromatography; HT, hydrotalcite; HTFA, triuoroacetic acid; ICP-AES, inductively coupled plasma-atomic emission spectroscopy; ILs, ionic liquids; LA,
levulinic acid; LAS-OH, Lewis acid site-OH; MA, maleic anhydride; MC, mesoporous carbon); MF, 2-methylfuran; MFA, methyl furoate; MFFA, 5-methylfurfuryl alcohol; MFF,
methyl 5-formyl-2-furoate; MFf, 5-methylfurfural; MIBK, methyl isobutyl ketone; [MIMPS]3PW12O40, 1-(3-sulfonic acid)propyl-3-methyl imidazolium phosphotungstate;
ML, methyl levulinate; MOF, metal organic framework; MSNs, mesoporous silica nanoparticles; MTHF, 2-methyltetrahydrahydrofuran; NA-p, niobium hydroxide treated
with 1 M phosphoric acid; NHC, N-heterocyclic carbene; oxoMAT, oxomatairesinol; P[BVIM]Cl, poly(3-butyl-1-vinylimidazolium chloride); PAL, pyruvic aldehyde; PBF, poly(butylene
2,5-furandicarboxylate); PMIM, propyl-3-methylimidazolium; POM, polyoxometalate; PON1, paraoxonase I; PVP, polyvinyl pyrrolidone; ROP, ring opening products; SA, suc-
cinic acid; SAPO, silicoaluminophosphate; SC, supercritical; SZ, sulfated zirconia; TA-p, tantalum hydroxide treated with 1 M phosphoric acid; TBAC, tetrabutylammonium
chloride; TEAB, tetraethylammonium bromide; TEMPO, 2,2,6,6-tetramethyl-piperidin-1-oxyl; TEOS, tetraethoxysilane; TGA, thermogravimetric; THF, tetrahydrofuran; THFA,
tetrahydrofurfuryl alcohol; TiZ, titania zirconia; TRS, total reducing sugar; TS, TiO2SiO2; VPO, vanadium phosphate; WCx, tungsten carbide; WP, tungsten phosphide; WZ,
tungstated zirconia; XPS, X-ray photoelectron spectroscopy; XRD, X-ray diffraction; ZrC, zirconium carbonate.
* Corresponding author. Biomass Group, College of Engineering, Nanjing Agricultural University, 40 Dianjiangtai Road, Nanjing, Jiangsu 210031, China. Tel.: +(86)025 58606570;
Fax: +(86)025 58606570.
E-mail address: zhenfang@njau.edu.cn; zhen.fang@mail.mcgill.ca (Z. Fang).

http://dx.doi.org/10.1016/j.pecs.2016.04.004
0360-1285/ 2016 Elsevier Ltd. All rights reserved.
H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194 99

Contents

1. Introduction ........................................................................................................................................................................................................................................................... 99
2. BronstedLewis acid bifunctionalized materials ................................................................................................................................................................................... 101
2.1. Synthesis of 5-hydroxymethylfurfural (HMF) from hexoses ................................................................................................................................................ 101
2.1.1. Supported ionic liquids (ILs) ........................................................................................................................................................................................... 102
2.1.2. Metal oxides ......................................................................................................................................................................................................................... 106
2.1.3. Modied heteropoly acids ............................................................................................................................................................................................... 108
2.1.4. Zeolites ................................................................................................................................................................................................................................... 108
2.2. Synthesis of furfural from pentoses ............................................................................................................................................................................................. 110
2.2.1. Molecular sieves ................................................................................................................................................................................................................. 110
2.2.2. Metal oxides ......................................................................................................................................................................................................................... 112
2.3. Synthesis of levulinic acid or levulinate esters ......................................................................................................................................................................... 112
2.3.1. Molecular sieves ................................................................................................................................................................................................................. 112
2.3.2. Resins and oxides ............................................................................................................................................................................................................... 114
2.4. Other methods and products .......................................................................................................................................................................................................... 115
2.4.1. Catalytic fast pyrolysis (CFP) for coke ......................................................................................................................................................................... 115
2.4.2. Phthalic anhydride ............................................................................................................................................................................................................. 116
2.4.3. 5-Ethoxymethylfurfural (EMF) ...................................................................................................................................................................................... 116
2.4.4. Alkyl lactates ....................................................................................................................................................................................................................... 117
2.4.5. Glycerol-derived chemicals ............................................................................................................................................................................................ 118
2.4.6. Oxygen-containing precursors for diesel and jet fuels ......................................................................................................................................... 118
3. Acidbase bifunctionalized materials ........................................................................................................................................................................................................ 119
3.1. HMF and furfural ................................................................................................................................................................................................................................. 120
3.2. HMF- and furfural-derivatives ........................................................................................................................................................................................................ 123
3.3. Biodiesel ................................................................................................................................................................................................................................................. 124
3.4. Other methods and biomass-derived chemicals ...................................................................................................................................................................... 125
3.4.1. Nanosized mixed oxides for obtaining isobutene from bio-ethanol ................................................................................................................ 125
4. Acid/basemetal bifunctionalized materials ........................................................................................................................................................................................... 125
4.1. Production of oxygenates ................................................................................................................................................................................................................. 125
4.1.1. Oxidation of sugars and polyols .................................................................................................................................................................................... 125
4.1.2. Oxidation of HMF and furfural ....................................................................................................................................................................................... 130
4.1.3. Oxidation of biomass derivatives to other oxygenates .......................................................................................................................................... 139
4.2. Production of hydrogenates ............................................................................................................................................................................................................ 142
4.2.1. Hydrolysishydrogenation of bio-polymers to polyols ......................................................................................................................................... 142
4.2.2. Hydrodeoxygenation of biomass derivatives with HMF as an intermediate ................................................................................................ 148
4.2.3. Hydrodeoxygenation of biomass derivatives with furfural as an intermediate ........................................................................................... 152
4.2.4. (Hydrolysis)hydrogenationcyclization of biomass derivatives to -valerolactone (GVL) ..................................................................... 157
4.2.5. Hydrogenation/hydrodeoxygenation of biomass derivatives to other hydrogenated products .............................................................. 165
5. Other bifunctional materials and catalytic routes ................................................................................................................................................................................. 168
5.1. Metals (Au, Ag, Cd, Ru, Pt, Pd, Cu, Ni) dispersed into nano-sized particles .................................................................................................................... 168
5.2. Cascade reactions with enzymes and electrocatalytic methods ......................................................................................................................................... 169
6. Auxiliary processes to boost catalytic eciency .................................................................................................................................................................................... 170
6.1. Biomass pretreatment ........................................................................................................................................................................................................................ 171
6.1.1. Molten salt hydrates and dual metal salts ................................................................................................................................................................. 171
6.1.2. Preoxidationhydrolysis ................................................................................................................................................................................................... 171
6.2. Reaction media .................................................................................................................................................................................................................................... 171
6.3. Control of functional materials ...................................................................................................................................................................................................... 172
6.3.1. Porosity .................................................................................................................................................................................................................................. 172
6.3.2. Surface polarity ................................................................................................................................................................................................................... 172
6.4. Heating modes including microwave and ultrasound ........................................................................................................................................................... 172
7. Conclusions and future outlook ................................................................................................................................................................................................................... 173
Acknowledgments ............................................................................................................................................................................................................................................ 174
References ............................................................................................................................................................................................................................................................ 174

1. Introduction catalytic upgrading of both syngas and bio-oil to transportation fuels


are in high demand [6,7]. At lower reaction temperatures (ca. 300 C),
Lignocelluloses composed of chitosan, lipids, microalgae, thermal processing of biomass with catalytic methods offers the pos-
macroalgae, polyols or polysaccharide and lignin units are the dom- sibility of selectively yielding a narrow range of products and to
inant biomass resources in the environment [1]. Microbial, reduce the energy requirements of the transformations [810]. Tra-
thermochemical, and chemical/catalytic processes are three main ditional catalytic strategies have relied mainly on mono-functional
approaches of converting biomass into energy, biofuels or chemi- materials for chemical transformations and while they are able to
cals [2]. Enzyme-mediated catalytic processes are the most common deliver the desired products for a wide range of substrates, they lack
way to produce bioethanol, butanol and biodiesel, in which pre- eciency when dealing with complex molecules [1113]. Bifunc-
treatment and post-treatment steps are used to remove compounds tional solid catalysts provide a method for eciently transforming
toxic to the microorganisms. Thermal processing of biomass gives complex substrates into products since they integrate sequential cata-
syngas via steam gasication by partial oxidation at temperatures lytic steps and avoid by-product formation and separation [1416].
from ~800 to 1000 C [3] or bio-oil via fast pyrolysis with or without In organic synthesis, bifunctional catalysis denotes simultane-
catalyst at temperatures of ~500 C [4,5]. Ecient processes for the ous activation of both partners of a bimolecular reaction [17].
100 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

Fig. 1. Reaction routes for the valorization of biomass with catalytic methods (L: Lewis, B: Bronsted, [H]: hydrogenation, [O]: oxidation, [HDO]: hydrodeoxygenation, FDCA:
2,5-furandicarboxylic acid, HMF: 5-hydroxymethylfurfural, EMF: 5-ethoxymethylfurfural, DMTHF: 2,5-dimethyltetrahydrofuran, FfA: furfuryl alcohol, DMF: dimethylfuran,
MF: 2-methylfuran, MTHF: 2-methyltetrahydrahydrofuran, MA: maleic anhydride, THF: tetrahydrofuran, LA: levulinic acid, GVL: -valerolactone).

Bifunctionality of solid catalysts implies that the materials serve not cellulose and hemicellulose can be selectively converted into
only as activators for chemical species, but also that they can ac- 5-hydroxymethylfurfural (HMF) and furfural, respectively [26].
tivate chemical species in a cascade of steps and possibly have The isomerization of sugars with a Lewis acid or a base catalyst
synergistic characteristics depending on the multi-step process acts as a vital bridge to connect polysaccharide hydrolysis and sub-
[18,19]. In other words, multiple catalytic steps are carried out in sequent monosaccharide dehydration, both of which can be
a single pot with bifunctional catalytic solid materials that are de- promoted by Bronsted and Lewis acids. The liquid fuel additive,
signed with the nal product in mind. The combination of multiple 5-ethoxymethylfurfural (EMF), can be synthesized via acid-catalyzed
synthetic, enzymatic, homogeneous/heterogeneous and electro- etherication [27]. Hydrogenation or hydrodeoxygenation (HDO) and
chemical catalytic systems in single pot operations, proceeding oxidation reactions are two major approaches to further upgrade
through sequential/tandem- and cascade/domino-type reactions, can biomass into biofuels and value-added chemicals. The introduc-
signicantly eliminate the isolation and purication of intermedi- tion of metal particles into upstream acid-mediated catalytic
ates and prevent the formation of unwanted by-products [20,21]. processes, in some cases, is capable of realizing chain reactions in
Bifunctional solid catalytic materials are designed to exploit en- a single pot. For example, HDO and oxidation of in situ generated
hanced selectivity of the target products so that processing is HMF from sugars are able to yield a liquid fuel 2,5-dimethylfuran
simplied. (DMF) or 2,5-dimethyltetrahydrofuran (DMTHF) [28], and a poten-
In lignocellulosic biomass, the rigid structural backbone of the tial monomer for plastics 2,5-furandicarboxylic acid (FDCA),
cell wall is formed by combination of cellulose microbrils with respectively [29]. However, competing reactions between oxida-
hemicelluloses joined via hydrogen bonds, and this is surrounded tion and dehydration such as glucose-to-gluconic acid oxidation
by resistant lignin sheaths that provide chemical and physical in- versus glucose-to-HMF-to-FDCA conversion, as well as between
tegrity against stress and degradation [2224]. Pretreatment of hydrogenation/HDO and dehydration like glucose-to-polyols hy-
lignocellulosic biomass with a physical, physicochemical, chemi- drogenation versus glucose-to-HMF-to-DMF transformation may
cal, biological and electrical methods alters its structure and allows proceed nonselectively. Likewise, the cascade production of four-
release of sugars in polymeric or oligomeric forms so that cata- or ve-carbon furanic compounds such as furfuryl alcohol (FfA),
lytic transformations can proceed eciently [25]. Fig. 1 illustrates 2-methylfuran (MF), 2-methyltetrahydrahydrofuran (MTHF), maleic
representative reaction routes for catalytic valorization of ligno- anhydride (MA), and tetrahydrofuran (THF) from xylose may also
celluloses. The distribution of products varies and is closely associated involve oxidation and hydrogenation of corresponding sugars. With
with the type of catalysts applied. In the presence of acid catalysts, levulinic acid (LA) as the key intermediate, both pentoses and hexoses
H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194 101

can be transformed into -valerolactone (GVL), which is consid- [53]. In this review, examples of one-pot multiple transformation
ered to be a potential fuel additive [30]. Most importantly, some of biomass into biofuels and valuable chemicals over different types
diesel fuels based on long-chain alkanes (C8C15) are able to be pro- of functional catalysts are presented. Emphasis is given on assess-
duced from the integration of coupling, condensation, and ing the bifunctionality of the catalytic materials and relevant
ketonization with subsequent hydrogenation of biomass-derived auxiliaries such as reaction media, heating modes, catalyst com-
molecules [31]. Catalytic oxidation, hydrogenation and HDO of pre- positions and texture/morphology properties, and compatibility of
treated lignin can correspondingly afford aromatic aldehydes, arenes various reactions. Plausible reaction mechanisms and pathways are
and cycloalkanes [32]. Some other biomass-derived species, like discussed for specic products and catalytic systems.
microalgae and chitosan, can be used advantageously to produce
biofuels [33,34]; in particular, the production of biodiesel can be 2. BronstedLewis acid bifunctionalized materials
achieved from simultaneous esterication and transesterication
of lipids catalyzed by Lewis/Bronsted dual acids or acid/base 2.1. Synthesis of 5-hydroxymethylfurfural (HMF) from hexoses
bifunctionalized materials [35], and with some post-treatment steps,
the major by-product glycerol can be used to produce carboxylic Ecient routes to HMF from six-carbon carbohydrates are im-
acids, esters, ethers, ketals/acetals, monohydric alcohols/diols, ac- portant for developing methods to process lignocellulosic biomass,
rolein, and alkanes/syngas through corresponding reaction routes since HMF is considered as a valuable precursor for the synthesis
of oxidation, esterication, etherication/oligomerization, ketalation/ of biofuels (e.g. DMF and DMTHF) and value-added chemicals such
acetalation, hydrogenolysis, dehydration, and pyrolysis/gasication as biopolymers [5458]. Relatively high HMF yields can be achieved
[36]. from fructose substrate catalyzed by Bronsted or Lewis acids.
Review articles on catalytic conversion of biomass report on re- However, when glucose or glucose-derived bi-/polysaccharide is used
action routes and potential substrates for the production of biofuels as the substrate, either low HMF selectivity or low substrate con-
[3740], catalytic performance for different catalysts [41,42], pro- version is observed in the presence of single Bronsted or Lewis acids
cessing methods [43,44], heterogeneous catalysis [4547], underlying [54,56,57]. Qian et al. [5961] demonstrated that Bronsted acids have
mechanisms [48,49], and environmental and economic analyses the capability to initiate both dehydration and isomerization reac-
[50,51]. An emerging trend for biomass valorization is to integrate tions of glucose through protonating the C2OH to form a common
the catalytic transformations, reaction engineering and product sep- 5-member ring intermediate, which implies that the formation of
aration [52] processes into a single operation, wherein design of the HMF occurs via a direct cyclic mechanism, rather than via the open
catalytic materials is considered as one of the key points for estab- chain mechanism that converts glucose to fructose and then to HMF
lishing ecient and environmentally-friendly processing systems (Fig. 2). HMF selectivities and yields from glucose are extremely

Fig. 2. Plausible pathways for glucose to 5-hydroxymethylfurfural (HMF) conversion mediated with Bronsted or Lewis acids.
102 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

Fig. 3. Polysaccharide-to-HMF (5-hydroxymethylfurfural) conversion via sequential hydrolysisisomerizationdehydration reactions.

sensitive to processing conditions using conventional Bronsted acid hydrogen species from the hydroxyl groups of cellulose. Weak ion-
dehydration processes [59]. The dehydration of glucose to HMF paired halide ions promote disruption of the otherwise extensive
begins from Lewis acidcatalyzed isomerization of glucopyranose network of intra and interchain hydrogen bonds of cellulose [74,75].
to fructofuranose [62,63], which can be further dehydrated into HMF However, interaction of CrCl2 with water results in the generation
with Lewis or Bronsted acid catalysts (Fig. 2) [6466]. The com- of stable and coordinative saturated [Cr(H2O)6]2+ complexes that sig-
bined use of Lewis and Lewis/Bronsted acids is considered to be an nicantly inhibit the catalytic activity of CrCl2. It is still dicult to
improved approach for selective and ecient transformation of recycle the metal chlorides although solvent extraction, vacuum dis-
glucose and glucose-based biopolymers into HMF via one-pot se- tillation, and N2 stripping have been proposed [48,56]. Homogeneous
quential isomerizationdehydration reactions. Wrigstedt et al. [67] catalysts require a recycle step that is time-consuming and energy-
illustrated the role of Bronsted acids in Lewis acidcatalyzed intensive so that their application in practical processes is limited.
aqueous-phase glucose dehydration to HMF, namely that the fruc- Ionic liquids (e.g., [BMIM]Cl and [EMIM]Cl) are considered to act
tose dehydration step could be accelerated by the addition of a not only as a basic mediator, but also as a ligand for chromium that
Bronsted acid (e.g. H3PO4, H2SO4, HNO3, and HCl) into a Lewis acid lessens the negative effect of water on HMF yield and promotes isom-
(CrCl36H2O)mediated system. A signicant retardation of the erization and dehydration of glucose into HMF [76]. Organic solvents
glucose conversion rate was observed due to the restrained forma- (e.g., DMSO and DMA) can facilitate the formation of HMF by sup-
tion of the chromiumglucose chelate complex during reaction, pressing the degradation of the furan ring, but separation by
which results in a substantial drop in the HMF yield. However, higher evaporation and reuse of the solvent are problematic. Aqueous cata-
reaction temperatures with systematical adjustment of pH areable lytic systems are preferable due to eciency, since in situ generated
to obtain high HMF yields (ca. 50%) and ecient conversions (ca. metal ion hydroxo complexes (metal-hydroxo complexes + n H+
90%). Choudhary et al. [68] demonstrated that Bronsted acidity metaln+ + n/2 H2O) seem to promote isomerization of glucose to fruc-
retards aldose-to-ketose isomerization, while Lewis acidity in- tose in the case of some metal salts (e.g., AlCl3) [77]. The introduction
creases the overall rate of consumption of fructose and HMF by of protonic acids not only increases the content of Bronsted acid
promoting side reactions. Furthermore, those authors indicated that sites to facilitate hydrolysis and dehydration reactions [78], but also
it would be possible to maximize product yield by optimizing the promotes the formation of metaln+ instead of metal-hydroxo com-
concentrations of Lewis and Bronsted acids as well as catalyst plexes (Fig. 3), thus hindering glucose isomerization which is the
structures/compositions in the cascade reactions. key step of transformation [77]. Therefore, the ratio/distribution of
Metal chlorides are considered as Lewis acids in 1-alkyl-3- Bronsted acid to Lewis acid sites must be adjusted to allow both
methylimidazolium chloride ionic liquids (ILs) and have been found the glucose-to-fructose isomerization and the hydrolysis/dehydration
to be effective for the conversion of sugars to HMF [6971], among step to proceed smoothly.
which chromium (II) chloride (CrCl2) is superior to others in the cata-
lytic process of glucose-to-HMF transformation, affording an HMF 2.1.1. Supported ionic liquids (ILs)
yield of nearly 70% at 100 C in 3 h [72]. For cellulose hydrolysis, Polysaccharides (e.g., cellulose) are dicult to be degraded via
CuCl2 dissolved in 1-ethyl-3-methylimidazolium chloride ([EMIM]Cl) simple heterogeneous catalysis that can be attributed to their strong
still displays high activity at 120 C, but the product HMF yield is intra- and inter- molecular hydrogen bonds and the existence of crys-
less than 10% [73]. In contrast, a pair of metal chlorides (CuCl2 and talline and amorphous regions. Unlike neutral ionic liquids, acidic
CrCl2) with CuCl2 mole fraction of 0.830.95 or a combination of CrCl2 ILs such as 1-(4-sulfonic acid)butyl-3-methylimidazolium hydro-
and RuCl3 (with a molar ratio of CrCl2/RuCl3 = 4/1) in [EMIM]Cl at gen sulfate ([SO3HBMIM]HSO4) exhibit higher activity for the
temperatures of 80120 C could collectively catalyze the single- hydrolysis of cellulose than protonic acids such as HCl, HNO3, H3PO4,
step process of converting cellulose to HMF in nearly 60% yield. The and H2SO4 (70% vs. 4060% conversion), and have improved cata-
synergistic effect of two different metal chlorides on catalytic con- lytic performance (8889% conversion) for producing HMF (37%
version of glucose units into HMF probably occurs due to the yield) and furfural (18% yield) among different ILs with the addi-
promotion of the cleavage of both - and -1,4-glucosidic bonds at tion of catalytic amounts of MnCl2 in a biphasic system consisting
comparable rates as well as glucose-to-fructose isomerization. Chlo- of H2O/MIBK (methyl isobutyl ketone) reaction system (Table 1,
ride ions of ionic liquids and metal chlorides are able to accept Entries 16) [79], in which the coordination effect of SO3H/SO42
Table 1
BronstedLewis acid bifunctional solid catalysts used in the conversion of carbohydrate substrates into 5-hydroxymethylfurfural with summary of reaction conditions, maximum catalytic activity, catalyst reusability and cat-
alyst preparation method.

Entry Substrate Catalysta Reaction condition Catalytic activity Reusability Catalyst preparation Ref.

Solvent Temp Time Conv Yield/ Cycles Yieldb Method Calcination Waste
[Selec]

1 Cellulose (25 wt%) 0.2 M MnCl2 + [SO3HBMIM]HSO4 MIBK 150 C 5h 89% 37% 5 >20% Co-condensation No IL + Mn2+ [79]
2 Cellulose (25 wt%) 0.2 M MnCl2 + [BMIM]BF4 MIBK 150 C 5h 5% 1% Co-condensation No Mn2+ [79]
3 Cellulose (25 wt%) 0.2 M MnCl2 + [BMIM]PF6 MIBK 150 C 5h 5% 1% Co-condensation No Mn2+ [79]
4 Cellulose (25 wt%) 0.2 M MnCl2 + [BMIM]Br MIBK 150 C 5h 4% <1% Co-condensation No Mn2+ [79]
5 Cellulose (25 wt%) 0.2 M MnCl2 + [BMIM]Cl MIBK 150 C 5h 11% 2% Co-condensation No Mn2+ [79]
6 Cellulose (25 wt%) 0.2 M MnCl2 + [BMIM]H2PO4 MIBK 150 C 5h 23% 8% Co-condensation No Mn2+ [79]
7 Glucose (10 wt%) 15 mol% GeCl4 [BMIM]Cl 100 C 1h 98% 38% 5 No Ge4+ [80]

H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194


8 Cellulose (50 wt%) [SO3HBMIM]HSO4 MIBK 150 C 5h 70% 15% Co-condensation No IL [81]
9 Cellulose (50 wt%) 0.2 M FeCl2 + [SO3HBMIM]HSO4 MIBK 150 C 5h 34 84 5 26% Co-condensation No IL + Fe2+ [81]
10 Cellulose (25 wt%) 0.2 M CoSO4 + [SO3HBMIM]HSO4 MIBK 150 C 5h 84% 24% 5 ~18% Co-condensation No IL + Co2+ [82]
11 Cellulose (5 wt%) 0.2 M CrCl36H2O + [SO3HPMIM]HSO4 [BMIM]Cl 120 C 5h 95% 53% 8 ~40% Co-condensation No IL + Cr3+ [83]
12 Cellulose (3.3 wt%) [SO3HPMIM]HSO4 DMSO 160 C 5h 25% Co-condensation No IL [84]
13 Cellulose (3.3 wt%) 0.04 M InCl3 + [SO3HPMIM]HSO4 DMSO 160 C 5h 85% 45% 5 ~30% Co-condensation No IL + In3+ [84]
14 Glucose (10 wt%) 10 mol% CrCl36H2O Et-DBUBS 110 C 2h 100% 83% 5 ~80% No IL + Cr3+ [85]
15 Glucose (3.3 wt%) [CO2HPMIM]Cl DMSO 120 C 7h 12% Co-condensation No IL [86]
16 Glucose (3.3 wt%) 0.2 M ZrOCl2 + [CO2HPMIM]Cl DMSO 120 C 7h 51% 6 Co-condensation No IL + Zr4+ [86]
17 Glucose (4 wt%) 10 mol% CrCl2 DMF 120 C 3h 50% Cr2+ [87]
18 Glucose (4 wt%) 10 mol% P[BVIM]ClCrCl2 DMF 120 C 3h 66% 6 ~38% Polymerization, No Cr2+ [87]
immobilization
19 Glucose (4 wt%) 10 mol% P[BVIM]ClAlCl3 DMF 120 C 3h 49% 6 ~38% Polymerization, No NMc [87]
immobilization
20 Glucose (5 wt%) 30 wt% SO3HPILPW DMSO 150 C 2h 18% Polymerization, No NM [88]
protonation
21 Glucose (5 wt%) 30 wt% SO3HPILPW/CrCl3 DMSO 150 C 2h 34% Polymerization, No Cr3+ [88]
protonation,
immobilization
22 Glucose (10 wt%) 10 mg H2O:DMSO/2-BuOH:MIBK 150 C 3h 50% 35%[70%] Post-grafting No Cr2+ [89]
CrCl2ImSBA-15
23 Fructose (30 wt%) 3.3 wt% TaaSBA-15 H2O/2-BuOH:MIBK 180 C 0.5 h 66% 49%[74%] Co-condensation, No NM [90]
protonation
24 Glucose (6.7 wt%) 100 wt% H+D001-cc
resin [BMIM]Cl 110 C 0.5 h 10% Ion exchange No NM [91]
25 Glucose (6.7 wt%) 100 wt% Cr3+D001-cc resin [BMIM]Cl 110 C 0.5 h 61% 6 40%, Ion exchange No Cr3+ [91]
~70%
(2nd)
26 Fructose (3 wt%) 26.7 wt% MSN DMSO 90 C 3h 27% 0 Co-condensation No NM [92]
27 Fructose (3 wt%) 26.7 wt% [HSO3 + (ILs/CrCl2)]MSN DMSO 90 C 3h 98% 73%[75%] 5 60%, Co-condensation, No NM [92]
73% post-grafting
(4th)
28 Glucose (5 wt%) 60 wt% CrHAP [BMIM]Cl 400 Wd 150 s 78% 40% 5 ~40% Impregnation 500 C NM [93]
29 Glucose (5 wt%) Sn-Mont THF-DMSO (7:3, v/v) 160 C 3h 98% 54% 6 ~53% Ion-exchange 600 C, 4 h NM [94]
30 Cellulose (5 wt%) Sn-Mont THF/H2ONaCl (5:1, v/v) 160 C 3h 39% Ion-exchange 600 C, 4 h NM [94]
31 Cellulose (5 wt%) 100 wt% ATPSO3HCr(III) [EMIM]Cl 120 C 2h 31% 5 22% Post-grafting, No Cr3+ [95]
impregnation
(continued on next page)

103
104
Table 1 (continued)

Entry Substrate Catalysta Reaction condition Catalytic activity Reusability Catalyst preparation Ref.

Solvent Temp Time Conv Yield/ Cycles Yieldb Method Calcination Waste
[Selec]

32 Cellulose (5 wt%) 100 wt% HNTsSO3HCr(III) [EMIM]Cl 120 C 2h 41% 5 22% Post-grafting, No Cr3+ [95]
impregnation
33 Cellulose (10 wt%) 100 wt% ZrO2 H2O 250 C 5 min ~20% ~6% Precipitation 550 C, 6 h NM [96]
34 Cellulose (10 wt%) 100 wt% SO4/ZrO2 H2O 250 C 5 min ~30% ~11% Precipitation 550 C, 6 h Sulfur [96]
Impregnation 550 C, 3 h
35 Fructose (0.3 wt%) 90 wt% SO4/ZrO2 hollow nanoshells DMSO 120 C 1h 64% Etching SiO2, 650 C, 6 h Sulfur [97]
impregnation
36 Fructose (5 wt%) 50 wt% porous PO4/TiO2 nanoparticles DMALiCl 140 Cd 5 min 44% 6 ~35% Slow evaporation 400 C, 6 h NM [98]
37 Glucose (5 wt%) 20 wt% porous H3PO4/TiO2 DMALiCl 140 Cd 5 min 22% Slow evaporation 400 C, 6 h NM [98]

H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194


nanoparticles
38 Sugarcane bagasse 20 wt% porous PO4/TiO2 nanoparticles DMALiCl 140 Cd 5 min 26% Slow evaporation 400 C, 6 h NM [98]
(5 wt%)
39 Fructose (1 wt%) 13.3 wt% 9.8WO3/ZrO2 H2O 130 C 4h [40%] Impregnation 700 C, 4 h NM [99]
40 Glucose (5 wt%) 2 wt% ZrMoSA [BMIM]Cl/H2O 150 C 3h 27% Sol-gel 600 C, 5 h NM [100]
41 Glucose (5 wt%) 50 wt% mesoporous TiO2 nanospheres DMALiCl 130 Cd 2 min 30% Self-assembly 500 C, 4 h NM [101]
42 Glucose (5 wt%) 50 wt% mesoporous TiO2 nanospheres DMSO 140 Cd 5 min 36% Self-assembly 500 C, 6 h NM [102]
43 Cellulose (8.8 wt%) 26.7 wt% mesoporous TiO2 [EMIM]Cl/H2O 120 C 3h 18% Self-assembly, 550 C, 6 h NM [103]
nanocatalyst hydrothermal
treatment
44 Cellulose (8.8 %) 26.7 wt% mesoporous ZrO2 [EMIM]Cl/H2O 120 C 3h 29% Self-assembly, 550 C, 6 h NM [103]
nanocatalyst hydrothermal
treatment
45 Glucose (2 wt%) 30 wt% nanosized PO4/TiO2 H2O/n-BuOH 175 C 3h 97% 81% 6 ~70% Sol-gel, 600 C, 4 h NM [104]
impregnation
46 Fructose (6 wt%) 71 wt% PO4/Nb2O5 (P/Nb = 2, w/w) H2O 100 C 0.5 h 29% [100%] Impregnation 255 C, 6 h NM [105]
47 Fructose (8 wt%) 100 wt% mesoporous PO4/Nb2O5 H2O 130 C 0.5 h 58% 45% 5 32% Sol-gel, 500 C, 5 h NM [106]
hydrothermal
treatment
48 Glucose (1 wt%) 100 wt% PO4/Nb2O5 H2O 120 C 3h 92% [52%] Precipitation, 100 C, 12 h NM [107]
impregnation
49 Inulin (6 wt%) 8.3 wt% PO4/Nb2O5 (NA-p) H2O/2BuOH (2:3, v/v) 160 C 80 min 76% 74% Impregnation 300 C, 3 h NM [108]
50 Glucose (10 wt%) 33.3 wt% PO4/Ta2O5 H2O/MIBK (3:7, v/v) 175 C 1.5 h 69% 23% Sol-gel 550 C, 3 h NM [109]
Impregnation 300 C, 2 h
51 Glucose (6 wt%) 8.3 wt% PO4/Ta2O5 (TA-p) H2O/2BuOH (2:3, v/v) 160 C 180 min 99% 90% 15 85% Impregnation 300 C, 3 h NM [110]
52 Glucose (6 wt%) 8.3 wt% PO4/Ta2O5 (TA-p) H2O/2BuOH (2:3, v/v) 160 C 140 min 70% 57% Impregnation 300 C, 3 h NM [110]
53 Glucose (10 wt%) 33.3 wt% mesoporous PO4/Ta2O5 H2O/MIBK (3:7, v/v) 170 C 1h 56% 33% 3 22% Sol-gel, 550 C, 6 h NM [111]
impregnation
54 Glucose (18 wt%) 55.6 wt% SnW oxide THF/H2O (5/1, v/v) 120 C 18 h 48% Co-precipitation 800 C, 3 h NM [112]
55 Glucose (10 wt%) 500 wt% DMSO 110 C 6h 100% 74% 4 ~70% Impregnation 450 C, 6 h NM [113]
SnVPO
56 Glucose (10 wt%) 10 wt% -Sr(PO3)2 H2O 220 C 5 min 60% 21% Precipitation 900 C, 3 h NM [114]
57 Glucose (10 wt%) 10 wt% CaP2O6 H2O 220 C 5 min 70% 20% Precipitation 900 C, 3 h NM [114]
58 Glucose (10 wt%) 33.3 wt% SO4/ZrMCM-550 H2O/MIBK (3:7, v/v) 175 C 2.5 h 82% 23% 4 ~15% Sol-gel 500 C, 6 h NM [115]
Impregnation 750 C, 2 h;
(continued on next page)
Table 1 (continued)

Entry Substrate Catalysta Reaction condition Catalytic activity Reusability Catalyst preparation Ref.

Solvent Temp Time Conv Yield/ Cycles Yieldb Method Calcination Waste
[Selec]

59 Glucose (10 wt%) 33.3 wt% AlMCM-550 20 wt% NaCl H2O/MIBK 195 C 0.5 h 98% 63% 3 ~45% Sol-gel 500 C, 3 h NM [116]
(3:7, v/v)
60 Glucose (30 wt%) 3.3 wt% Ag3PW12O40 H2O/MIBK (1:2.25, v/v) 130 C 4h 89% 76% 6 ~70% Precipitation 200 C, 12 h NM [117]

H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194


61 Sucrose (10 wt%) 10 wt% AgSTA H2O 120 C 160 min 92% 63% 8 ~60% Precipitation 120 C, 12 h NM [118]
62 Fructose (30 wt%) 21.3 wt% Cs2.5H0.5PW H2O/MIBK (1:3, v/v) 115 C 1h 95% 74% 6 ~67% Precipitation No NM [119]
63 Cellulose (5 wt%) 5 mol% Cr[(DS)H2PW12O40]3 H2O 150 C 2h 77% 53% Precipitation No NM [120]
64 Glucose (15 wt%) 5.9 mol% C16H3PW11CrO39 H2O 130 C 2h 84% 35% 6 ~34% Precipitation No NM [121]
65 Glucose (2.5 wt%) 83 wt% H-Beta (Si/Al: 15)-750 H2ODMSO (9:1)/THF 180 C 3h 78% [55%] 5 40% Dealumination 750 C, 1 h NM [122]
(1:3)
66 Glucose (10 wt%) 40 wt% H-Beta (Si/Al: 25) [BMIM]Cl 180 C 50 min 81% 50% 6 36% Dealumination 550 C, 5 h NM [123]
67 Cellulose (2.5 wt%) 200 wt% HZSM-5 (Si/Al: 37) H2O 190 C 4h 67% 46% 5 ~40% Desilication 550 C, 5 h NM [124]
68 Glucose (10 wt%) 0.5 mol% Sn-Beta 1-Butanol + H2O + 35 wt% 160 C 1.5 h 75% 14%/[18%] Dealumination 550 C, 5 h NM [125]
NaCl
69 Glucose (10 wt%) HCl (pH = 1) 1-Butanol + H2O + 35 wt% 160 C 1.5 h 26% 10%/[40%] No Acid [125]
NaCl
70 Glucose (10 wt%) HCl (pH = 1) 0.5 mol% Sn-Beta 1-Butanol + H2O + 35 wt% 160 C 1.5 h 75% 41%/[55%] Dealumination 550 C, 5 h Acid [125]
NaCl
71 Glucose (10 wt%) HCl (pH = 1) 0.5 mol% Sn- H2O 160 C 1.5 h 45% 2.7%/[6%] Dealumination 550 C, 5 h Acid [125]
Beta
72 Glucose (10 wt%) HCl (pH = 1) 0.5 mol% Sn-Beta 1-Butanol + H2O 160 C 1.5 h 77% 20%/[26%] Dealumination 550 C, 5 h Acid [125]
73 Glucose (10 wt%) HCl (pH = 1) 0.5 mol% Sn-Beta THF + H2O + 35 wt% NaCl 160 C 1.5 h 79% 57%/[72%] Dealumination 550 C, 5 h Acid [125]
74 Glucose (2 wt%) 3.3 wt% Amberlyst-70 3.3 wt% Sn-Beta GVL/H2O (9:1, w/w) 130 C 0.33 h 92% 59%/[64%] Dealumination 550 C, 5 h NM [126]
75 Glucose (2 wt%) 3.3 wt% Amberlyst-70 3.3 wt% GVL/H2O (9:1, w/w) 130 C 0.25 h 90% 46%/[51%] Dealumination 550 C, 5 h NM [126]
SnSBA-15
76 Glucose (2 wt%) 3.3 wt% Amberlyst-70 3.3 wt% Sn-Beta THF/H2O (9:1, w/w) 130 C 0.5 h 90% 63%/[70%] Dealumination 550 C, 5 h NM [126]
77 Glucose (2 wt%) 3.3 wt% Amberlyst-70 3.3 wt% THF/H2O (9:1, w/w) 130 C 0.33 h 90% 36%/[40%] Dealumination 550 C, 5 h NM [126]
SnSBA-15
78 Glucose (2 wt%) 3.3 wt% Amberlyst-70 3.3 wt% Sn-Beta MTHF:THF/H2O (9:1, 130 C 0.67 h 90% 59%/[66%] Dealumination 550 C, 5 h NM [126]
w/w)
a
Catalyst dosage relative to substrate.
b Yield of 5-HMF in the last cycle.
c NM: not mentioned.
d Microwave heating. SA: succinic acid, DS: dodecyl sulfate, NA-p: niobium hydroxide treated with 1 M phosphoric acid and calcined at 300 C, TA-p: tantalum hydroxide treated with 1 M phosphoric acid and calcined at

300 C, VPO: vanadium phosphate, AlMCM-550: aluminum containing MCM-41 molecular sieve calcined at 550 C, STA: silicotungstic acid, H-ZSM-5: a protonic zeolite, Amberlyst 70: a macroporous polymer catalyst, Sn-
Beta: a modied zeolite, SnSBA-15: a mesoporous molecular sieve, PMIM: propyl-3-methylimidazolium; MIBK: methyl isobutyl ketone, DMSO: dimethylsulfoxide, DBUBS: DBU-based (DBU: 1,8-diazabicyclo[5.4.0]undec-7-
ene) ILs with the benzene sulfonate (BS) anion.

105
106 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

Fig. 4. Synthetic route for preparation of SBA-15 supported bifunctional acid catalyst. Adapted with permission from Refs. 90 and 127, Copyright 2011, American Chem-
ical Society; Copyright 2010, Springer.

with moderate acidity and MnCl2 occurs to promote cascade cel- choosing an appropriate solvent, the degree of ion exchange and
lulose hydrolysis and glucose dehydration reactions eciently. By swelling of the support can be lessened that is helpful to some extent
employing SO3H or COOH-functionalized IL as the Bronsted acid in lowering the leaching of active sites to a few percent. In the aqueous
counterpart, a series of other related metal chlorides including GeCl4, phase, the leaching of IL in small amounts is detected, but it does
FeCl2, FeCl3, CoCl2, ZnCl2, CuCl2, NiCl2, InCl3 and CrCl3 catalyze the not seem to perturb the reaction (Table 1, Entry 22) [89].
transformation of carbohydrates especially cellulose to HMF with By using a co-condensation method [90,127], a Lewis/Bronsted
high yields (Table 1, Entries 716) [8086]. Strong Bronsted acid ILs acid bifunctional mesoporous catalyst (Taa-SBA-15) can be pre-
seem to be necessary for the hydrolysis of cellulose, while metal pared by incorporating 3-((3-(trimethoxysilyl)propyl)thio) propane-
chlorides are active for the subsequent dehydration of glucose to 1-sulfonic acid into SBA-15-type silica (Fig. 4) that shows good
HMF. However, the recycle of acidic ILs tends to be complicated, since activity in the dehydration of aqueous fructose after a short time
water remains in the IL phase that leads to rehydration of HMF and of 0.5 h (Table 1, Entry 23), which is capable of affording a higher
the formation of LA. selectivity to HMF (71%, with 84% conversion) than its sulfone de-
To improve the recyclability of IL-based catalytic systems, a series rivative at 130 C after 141 min. The superior catalytic performance
of heterogeneous BronstedLewis acid bifunctional materials have might be due to the hydrophobic nature as well as the promoting
been proposed (Table 1). Liu and Chen [87] used a polymeric IL (PIL) effect of Lewis acid thioether groups of Taa-SBA-15 on the
as a catalyst support for catalyst recovery as well as biomass con- tautomerization of fructose to its furanose [90,127]. As evidence for
version, and found that poly(3-butyl-1-vinylimidazolium chloride) this, it has been reported that D001-cc resin having Bronsted acid-
(P[BVIM]Cl) is effective for glucose-to-HMF conversion with up to rich sites is favored for the dehydration of fructose but it lacks Lewis
66% yields being obtained at 120 C for 3 h when combined with acid sites for conversion of glucose to HMF [128]. As an improved
CrCl2 in situ or used as the prebuilt PIL metalate P[BVIM]+[CrCl3] in approach, the D001-cc resin modied with Cr3+ can be obtained by
DMF (Table 1, Entries 1719). The P[BVIM]ClCrCl2 catalyst remains simple ion-exchange, in which it is found that the material con-
effective for the two-step transformation of cellulose into HMF cov- verts glucose into HMF with a yield of 61% in [BMIM]Cl at 110 C
ering cellulose-to-glucose conversion through controlled hydrolysis in 30 min (Table 1, Entries 24 and 25) [91]. In that work [91], the
in [EMIM]Cl, and then by adding the PIL-based catalyst for subse- HMF yields in two recycle tests were higher than that in the rst
quent dehydration of glucose, achieves 50% HMF yield at 120 C. The run, which might be the result of formation of CrCl4 with the IL
analogous P[BVIM]ClAlCl3 catalyst is less effective than the PILCr or incomplete washing of residual substrate from the catalyst. Al-
system in glucose-to-HMF conversion (HMF yield: 49% vs. 66%), but though ICP-AES (inductively coupled plasma-atomic emission
recycle tests show that the PILAl system is more robust because spectroscopy) shows the existence of leached elemental Cr in the
less metal leaching occurs that allow an HMF yield of 42% to be ob- solution, examination of solids with TGA (thermogravimetric anal-
tained for an average of 6 cycles. Immobilizing Cr3+ with SO3H- ysis) and EDX (energy-dispersive X-ray spectroscopy) for adsorbed
functionalized solid PILs bearing counter anions such as Cl and chemical species and surface complexes show that some species
PW12O403 (i.e., SO3HPILCl/CrCl3 and SO3HPILPW/CrCl3) is found cannot be simply washed off so that method development is needed
to be effective for selective transformation of carbohydrates espe- to allow reliable assessment of catalyst reusability.
cially glucose into HMF [88]. In comparison to chloridion, the presence Other porous solids supported BronstedLewis acid bifunc-
of the heteropoly anion is able to enhance the hydrophobicity of tional catalysts such as mesoporous silica nanoparticles (MSNs)
the PIL catalyst and the relatively low activation energy (22.02 kJ mol1) functionalized with both sulfonic acid and IL ([HSO3 + (ILs/CrCl2)]-
demonstrates its high catalytic performance in the production of MSN) (Table 1, Entries 26 and 27) [92], hydroxyapatite supported
HMF from carbohydrates (Table 1, Entries 20 and 21). Providing a chromium chloride (Cr-HAP) (Table 1, Entry 28) [93], tin hydroxide
local reaction microenvironment via immobilization on a solid porous nanoparticles-embedded montmorillonite (Sn-Mont) (Table 1, Entries
support is thought to allow coordination in the IL medium. For 29 and 30) [94], and acid-chromic chloride functionalized natural
example, Degirmenci et al. [89] introduced CrCl2 into an IL propyl- clay particles including treated attapulgite (ATP) and halloysite
3-methylimidazolium chloride ([PMIM]Cl) supported on the surface nanotubes (HNTs) (ATPSO3HCr(III) and HNTsSO3HCr(III))
of SBA-15 that lead to the formation of loosely bound, catalytically (Table 1, Entries 31 and 32) [95], as well as porous polymerized solid
active Cr2+ species. The resulting high mobility of these complexes acids [129,130] and bio-carbon-based solid acids [131,132] have been
(CrCl2ImSBA-15; Im refers to immobilized imidazolium-based explored for the carbohydrate-to-HMF transformation (Table 1). Aux-
IL) is found to be benecial for selective glucose dehydration, and iliary weak acidic groups like OH and COOH along with robust
affords an HMF selectivity of 70% for a glucose conversion of 50% in Lewis/Bronsted acid sites of functionalized materials are respon-
H2O:dimethylsulfoxide (DMSO)/2-BuOH:MIBK at 150 C for 3 h sible for the enhanced catalytic activities shown in Table 1.
(Table 1, Entry 22). The stability of CrCl2ImSBA-15 strongly
depends on the actual composition of the reaction medium, in par- 2.1.2. Metal oxides
ticular, DMA used as solvent reduces the Cr leaching to 30%. From the point of view of cost, metal oxides, such as ZrO2- and
Complexing of DMA with Cr is likely to relieve the interaction of TiO2-solid catalysts, are good candidates for biomass conversion
Cr2+ chloride with water to form coordinatively saturated [Cr(H2O)6]2+ (Table 1). Nevertheless, only low to moderate HMF yields have been
complexes that are inactive for HMF production from glucose. By achieved from saccharides for unmodied ZrO2 and TiO2 catalysts
H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194 107

Fig. 5. A silylation procedure leading to deactivation of unselective Lewis acid sites in conversion of glucose to 5-hydroxymethylfurfural (HMF). Adapted with permission
from Ref. 140, Copyright 2013, Elsevier.

[133]. Three major routes have been developed to enhance the cata- activity (90%, 58%, 87% and 5079% HMF yields obtained from fruc-
lytic performance of ZrO2 and TiO2 catalysts for carbohydrate-to- tose, glucose, inulin and juice of Jerusalem artichoke tuber,
HMF conversion (Table 1, Entries 3344): (1) modication of ZrO2 respectively) in aqueous biphasic systems (e.g. H2O/MIBK, H2O-2-
and TiO2 with strong Bronsted acids such as H2SO4 and H3PO4 to in- butanol). Ordomsky et al. [140] demonstrated that the reactivity of
corporate Bronsted acid sites [9698,134], (2) deposition of Zr or glucose conversion decreases in the order of niobium phosphate
Ti together with other metals like W and Mo bearing strong acidity (NbPO) > zirconium phosphate (ZrPO) > titanium phosphate
[99,100,135,136], (3) creation of porous and nano-sized ZrO2 and (TiPO) > aluminum phosphate (AlPO), corresponding to the amount
TiO2 materials to make the sites more accessible to substrates of strong acid sites on these catalysts. It was found that the selec-
[101103]. Thermal stability of the materials can be enhanced by tivity to HMF varies in the range of 3060% and increases with the
the metalOP bond formation (Table 1, Entry 45) [104]. decrease in the ratio of Lewis to Bronsted acid sites and the density
Due to strong acidic properties and high stability for acid cata- of isolated Lewis acid sites. Treatment of the catalyst with
lytic reactions in aqueous solution, Ta2O5 and Nb2O5 derived catalysts tetraethoxysilane (TEOS) decreased the content of isolated Lewis
have been investigated to produce HMF from various substrates in- acidity (Fig. 5), leading to a drastic increase in the selectivity toward
cluding monosaccharides and polysaccharides in water, however, HMF owing to the coverage of Lewis acid sites that is non-selective
the HMF yields obtained have not been very encouraging (Table 1, for the desired reaction process. The reaction mechanism was pro-
Entries 46 and 47) [105,106,137,138]. Nakajima et al. [107] illus- posed to occur via the adsorption of the carbohydrate substrate (e.g.,
trated that Lewis acid sites (NbO4 tetrahedra) on the Nb2O5nH2O glucose) onto the Lewis acid site for isomerization, followed by de-
surface immediately form NbO4H2O adducts in the presence of hydration over an adjacent phosphate group to give HMF.
water and a part of the adducts are able to function as effective Lewis After screening a series of heterogeneous and homogeneous cata-
acid sites that promote HMF formation from glucose (Table 1, Entry lysts including SnO2, WO3, SO2 + WO3, SnW oxide, Amberlyst-15,
48) but simultaneously giving the formation of complex polymers Naon NR-50, sulfated zirconia, H-mordenite, HY, H 2 SO 4 ,
that could not be readily analyzed by HPLC (high-performance liquid H3PW12O40, and hydrotalcite (HT), Yamaguchi et al. [112] found that
chromatography) or GCMS (gas chromatographymass spectrom- only SnW oxide bearing both strong Bronsted (97 mol g1) and
etry) [139]. H3PO4-treated Nb2O5nH2O (H3PO4/Nb2O5nH2O) leads to Lewis acid sites (37 mol g1) [141,142] are active for both glucose
a large decrease in undetectable products and an increase in HMF isomerization and fructose dehydration, such that HMF yields of 48%,
yield from 12% to 52% for the case of glucose-to-HMF transforma- 39%, 42%, and 41% are achieved in THF/H2O (5/1, v/v) at 120 C after
tion. It was speculated that most of the phosphate ions are xed 18 h from glucose, cellobiose, sucrose, and starch, respectively
as neutral OH groups on Nb2O5nH2O without covering Lewis acid (Table 1, Entry 54). Behera and Parida [113] prepared different weight
sites, which might reduce undesirable side reactions [107]. Another percentages (wt.%) of Sn-promoted vanadium phosphate (VPO) cata-
possibility is that NbO4 tetrahedra species having effective posi- lysts by a wet-impregnation method using water as the solvent, and
tive charges as Lewis acid sites are still active in water even after the 20 wt% SnVPO afforded an HMF yield of 74% from glucose in
the formation of NbO4H2O adducts. DMSO at 110 C for 6 h (Table 1, Entry 55). The presence of both
In the water-2-butanol (2:3, v/v) biphasic system, niobic acid Lewis and Bronsted acid sites in SnVPO plays an important role
treated with 1 M phosphoric acid and calcinated at 300 C (abbre- in the two reaction processes involving isomerization and dehy-
viated as NA-p) gives materials with large surface area and strong dration in the one-pot reaction system. Without regeneration at high
acidic properties providing effective activity for dehydration of mono- temperatures, the SnVPO catalyst separated by centrifugation and
saccharides to HMF as well as hydrolysis of polysaccharides to give thoroughly washed with acetone could be reused four times with
HMF yields of 89% and 74% successively from fructose and inulin almost constant HMF yields of ~70%. Alkaline earth phosphates in-
via a one-pot reaction (Table 1, Entry 49) [108]. Several modied cluding calcium and strontium (i.e., CaP2O6 and -Sr(PO3)2) with same
tantalum oxide catalysts including mesoporous tantalum oxide pre- acid strength in the range of +3.3 H0 +4.8 prepared through a
pared by acid hydrolysis of tantalum penta-ethoxide in the presence modied co-precipitation method have been employed as hetero-
of a triblock co-polymer Pluronic L-121 (a non-ionic surfactant) at geneous catalysts for the transformation of sugars (e.g., fructose,
room temperature and subsequent calcination at 550 C for 6 h glucose, and cellulose) to HMF in hot compressed water (200
(Table 1, Entry 50) [109], hydrated tantalum oxide treated with 1 M 230 C) [114]. In the hydrothermal system, both phosphate catalysts
H3PO4 and calcined at 300 C for 3 h (Table 1, Entries 51 and 52) [110], show similar catalytic reactivity toward the dehydration of mono-
and mesoporous tantalum phosphate prepared from tantalum tar- saccharides after reacting for 5 min, providing HMF yields of 34
trate and ammonium phosphate monobasic in the presence of an 39% and 2021% from fructose at 200 C and glucose at 220 C
ionic surfactant at room temperature followed by calcination at (Table 1, Entries 56 and 57), respectively, whereas the total yield
550 C (Table 1, Entry 53) [111] exhibits high specic surface area, of HMF and glucose from the catalytic hydrolysis and dehydration
strong acidity and remarkable stability, as well as high catalytic of cellulose at 230 C for 5 min with -Sr(PO3)2 (34%) is higher than
108 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

that with CaP2O6 (17%). Incorporation of metals such as Zr and Al acidity of Cr[(DS)H2PW12O40]3 was considered to stem from the elec-
into mesoporous acidic solid supports like MCM-41 and TUD-1 can tron pair acceptor metal cation (Cr3+), and Bronsted acidity was
give bifunctional solid catalysts that possess both Bronsted and Lewis generated from some protons of PTA molecules. The addition of sur-
acid sites that have high surface areas, for which approximately 30% factant DS to the CrHPA-based solid acid helps the assemble of
HMF yields have been obtained (Table 1, Entries 58 and 59) micelles in water solutions, by providing a hydrophobic environ-
[115,116,143]. ment sucient for protecting HMF from further decomposition and
by restricting formation of by-products. It was shown that 53% HMF
2.1.3. Modied heteropoly acids yield with 77% conversion is obtained directly from cellulose
Modication of heteropoly acids (HPAs) with large monovalent in aqueous medium at 150 C in 2 h (Table 1, Entry 63). The
cations such as Cs+ and Ag+ can overcome their limitations such as Cr[(DS)H2PW12O40]3 had remarkable stability for approximately six
high solubility in water and in polar solvents, low surface area and cycles after being subjected to hot CH2Cl2 extraction prior to each
poor thermal stability to allow the design of a range of insoluble, recycle trial. The same research group designed an analogous
microporous solid Lewis acid catalysts [144]. Shimizu et al. [145] BronstedLewissurfactant-combined cetyltrimethyl ammonium salt
reported on the use of FePW12O40 and Cs2.5H0.5PW12O40 for fructose of polyoxometalate substituted with a transition metal (Cr3+ )
conversion in DMSO to give HMF yields of 100% and 9197%, re- [C16H3PW11CrO39 (C16: cetyltrimethyl ammonium)] [121]. Owing to
spectively at conditions of 120 C and 2 h. Water was removed during the formation of micellar assembles with favorable hydrophobic sur-
the process, which apparently suppresses undesired reactions in- roundings, a high concentration of substrate could exist around the
cluding the hydrolysis of HMF to LA and partial dehydration of catalytic sites, although lower conversions of HMF were observed.
intermediates to condensation products. The removal of adsorbed In the process of catalytic transformation of glucose and fructose
water from the surface and near-surface of the catalyst can possi- into HMF, C16H3PW11CrO39 shows high conversion rates (84% and 90%,
bly be enhanced by decreasing the catalyst particle size. Fan et al. respectively) and good yields (35% and 41%, respectively) in water
[117] found Ag3PW12O40 exhibits both Bronsted and Lewis acidi- at 130 C (Table 1, Entry 64). Furthermore, the catalyst is able to be
ties by pyridine adsorption infrared spectroscopy. Using water/ recovered by centrifugation from the reaction mixture with a leach-
MIBK (1/2.25, v/v) as reaction medium, this bifunctional catalyst ing rate of 0.4% as measured by ICP-AES, and it can be reused for
proved to be suitable for the dehydration of glucose into HMF with six times with fructose conversion rates and HMF yields for all runs
a yield of 76% at 130 C for 4 h, and could be reused for up to six remaining around 90% and 40%, respectively. Several factors in-
reaction cycles with low leaching (5.1%) of Ag3PW12O40 (Table 1, Entry cluding the coexistence of both Lewis and Bronsted acid sites in the
60). Acidity modied silver exchanged silicotungstic acid (AgSTA) catalyst and the micellar structure containing hydrophobic groups
catalyst catalyzes sucrose degradation (92%) in superheated water in coordination contribute to the high catalytic activity.
to afford HMF in a yield of 63% at 120 C in 160 min (Table 1, Entry
61) [118] and an HMF yield of 74% with a selectivity of 95% for fruc- 2.1.4. Zeolites
tose in the presence of Cs2.5H0.5PW12O40 catalyst in a biphasic system With respect to sulfated zirconia supported over mesoporous
consisting of water and MIBK in 60 min at 115 C (Table 1, Entry 62) silica (SBA-15) and homogeneous HPAs, Lanzafame et al. [148] dem-
[119]. Notably, only trace amounts of metal leaching determined onstrated that microporous materials exhibited higher selectivity/
by UVvis spectrometry and constant HMF yields are detected for yields of glucose and HMF from cellulose because of the presence
these polyoxometalates after being reused for several times. The high of shape-selectivity effects that limit the polymerization of prod-
durability of the catalyst can be ascribed to its negligible solubili- ucts that form humic-type species. As an example, zeolites composed
ty in water and organic solvents as well as to the stable structure of SiO4 and [AlO4] tetrahedral are generally covered with micropores,
of Keggin-type PW12O403 ions. in which the negative charge of [AlO4] tetrahedral compensated with
An HPA salt of an IL-forming cation functionalized with H+ gives zeolites high acidity [149]. An IL/zeolite/CrCl2 system was
propanesulfonate, 1-(3-sulfonic acid)propyl-3-methyl imidazolium reported to be ecient for selectively producing HMF (48% yield)
phosphotungstate ([MIMPS]3PW12O40), was synthesized, and used from cellulose at 120 C via sequential hydrolysis and dehydration
as a reaction-induced self-separating catalyst in the conversion (Fig. 6) [150]. Nevertheless, the imidazolium based ILs are expen-
of fructose to HMF [146]. An HMF yield of 99% is realized when the sive and CrCl2 is hazardous to the environment. Jadhav et al. [151]
reaction is conducted in 2-butanol for 2 h at 120 C. Phosphotung- replaced the chromium salt with H-ZSM-5 zeolite to achieve a 45%
stic acid, H3PW12O40 (PTA), encapsulated in MIL-101 (a chromium yield of HMF from glucose in [BMIM]Cl at 110 C after 8 h. More-
terephthalate-based mesoscopic metal-organic framework) was also over, the IL solvent could be substituted with a non-toxic ammonium
evaluated as an ecient heterogeneous catalyst for the selective de- salt, tetrabutylammonium chloride (TBAC), to give an even higher
hydration of fructose to HMF (63% yield within 60 min) in [EMIM]Cl HMF yield of 56% at 110 C within 4 h.
at 80 C, although the catalytic system was ineffective for glucose- To improve the catalytic performance of Beta zeolite for the direct
to-HMF conversion [147]. Other catalytic functionalities like Lewis transformation of glucose into HMF, Otomo et al. [122] examined
acid or base sites are likely to be required for the achievement of the effects of calcination and steam treatment on the structure of
high HMF yields from glucose. Al atoms in the framework and its acidic properties. It was found
Zhao et al. [120] prepared a BronstedLewissurfactant-combined that the amount of Lewis acid sites increases at the expense of
HPA Cr[(DS)H2PW12O40]3 (DS: dodecyl sulfate) as a heterogeneous Bronsted acid sites by partial cleavage of SiOAl bonds in the
catalyst for the one-pot conversion of cellulose to HMF. The Lewis framework to form Al species out of the *BEA framework, when the

Fig. 6. Conversion of cellulose to HMF (5-hydroxymethylfurfural) over NHCmetal/zeolite catalysts in IL. Adapted with permission from Ref. 150, Copyright 2011, Elsevier.
H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194 109

Fig. 7. Schematic of glucose-to-HMF (5-hydroxymethylfurfural) dehydration over H-Beta zeolite calcined at 750 C. Adapted with permission from Ref. 126, Copyright
2014, Elsevier.

ammonium-type Beta is calcined at temperatures greater than 700 C properties such as total surface area, pore volume/size and acidity,
or is treated with steam (50 kPa in N2 balance) at temperatures more and allow the development of robust catalysts for producing
than 500 C. These bifunctional catalysts bearing Lewis acid sites HMF.
are effective for the production of HMF from glucose, and H-Beta Sn-Beta zeolite has been reported to facilitate the isomeriza-
(Si/Al: 15) prepared by calcination at 750 C shows a high HMF se- tion of glucose to fructose in aqueous media even at low pH
lectivity (55%) at 78% conversion of glucose in H2ODMSO/THF [152,153]. Nikolla et al. [125] described the combination of Sn-
reacting at 180 C for 3 h (Table 1, Entry 65). With 13C NMR, the Beta with a Bronsted acid HCl in a biphasic reactor system (H2O/
authors claried that glucose molecule are rst isomerized to fruc- THF or H2O/1-butanol) to synthesize HMF from carbohydrates such
tose through an intramolecular hydride transfer, and the generated as glucose (Fig. 8), cellobiose, and starch with HMF selectivities over
intermediate is subsequently dehydrated to HMF over Bronsted acid 70% at sugar conversions of around 75% at 180 C. For Sn-Beta, the
sites (Fig. 7). The Beta zeolite catalyst could be recovered by ltra- addition of HCl to give a solution pH to 1 affords an improved HMF
tion and regenerated by simple calcination and the HMF yield varied yield (Table 1, Entries 6870). The addition of inorganic salts (es-
from 43% to 40% for ve consecutive runs. Employing [BMIM]Cl as pecially NaCl) results in ecient extraction of HMF from the aqueous
the reaction medium, H-Beta zeolite with a moderate Si/Al ratio of phase to the organic phase, thus improving HMF selectivity (Table 1,
25 has high catalytic activity due to the presence of Bronsted and Entries 7073). Combination of a solid Bronsted acid Amberlyst-
Lewis acid sites of the material that are in a suitable ratio (1.03), 70 (a macroporous polymeric catalyst) with a Lewis acid Sn-SBA-
leading to 50% HMF yield with 81% glucose conversion (Table 1, Entry 15 (a mesoporous molecular sieve) or Sn-Beta for HMF synthesis
66) [123]. Furthermore, the combined use of H-Beta (Si/Al: 25) and from sugars in a monophasic system using -lactones, THF or THF/
[BMIM]Cl allows multiple recycle with non-varying HMF yields after MTHF with water in a weight ratio of 9:1 affords high selectivity
calcination at moderate conditions and is ecient for transforma- for HMF (up to 70%) at glucose conversions of ~90% at 130 C in 15
tion of other di- and poly-carbohydrates such as sucrose, cellobiose, 60 min (Table 1, Entries 7478) [126]. Although water is known to
starch and cellulose into HMF with consistent yields (ca. 45%). Apart promote side reactions in the dehydration of carbohydrates, it can
from dealumination of zeolites, bimodal-HZ-5 zeolite (Si/Al: 30.15) be benecial at low concentrations for increasing the solubility of
with a Bronsted/Lewis acid ratio of 0.817 fabricated by modica- sugars in the reaction phase. The effectiveness of glucose isomeri-
tion of H-ZSM-5 (Si/Al: 37.00) with desilication is also ecient for zation by the catalyst can be speculated to control the HMF
the hydrolysis of microcrystalline cellulose to HMF [124]. The post- selectivity, which is determined by the extent of fructose forma-
synthesized heterogeneous catalyst exhibits improvement in total tion in different solvents (i.e., THF > THF/MTHF GVL) [126]. Although
surface area, total pore volume and total acidity as compared with Sn-Beta predominantly isomerizes glucose to fructose via 1,2-
the parent H-ZSM-5, and enhanced HMF yields of 46% for a cellu- intramolecular hydride shift in both water and alcohol (e.g.,
lose conversion of 67% can be obtained (Table 1, Entry 67). It is clear methanol), Lewis acidic open Sn sites with Na-exchanged silanol
that the modication of commercial zeolites through either groups instead of proximal silanol groups are active for glucose
dealumination or desilication allow improvement of material mannose epimerization [154]. Therefore, an appropriate choice of

Fig. 8. Sn-Beta combined with Bronsted acid sites for glucose-to-HMF (5-hydroxymethylfurfural) dehydration.
110 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

Fig. 9. Lewis/Bronsted acid catalyst mediated xylose-to-furfural conversion. Adapted with permission from Ref. 158, Copyright 2011, American Chemical Society.

solvents and catalytic materials with well-controlled functional sucient pore volume (0.70 cm3/g) and acidity (10 mol/g surface
groups/sites are crucial to obtain desired products in high yields. acidity with a high Lewis/Bronsted acid sites ratio of ~15/1) [163].
Incorporation of niobium into MCM-41 with Si/Nb molar ratios of
2.2. Synthesis of furfural from pentoses either 25 or 50 (Lewis/Bronsted acid sites ratio: ~1/58) has higher
reactivity for xylose conversion (up to 99%) but lower selectivity to
Among various bio-derived furan-type compounds, furfural is a furfural (39%) in toluene/H2O (7:3, v/v) (Table 2, Entry 5), the formed
building-block chemical since its derivatives like MF, MTHF, THF, and terminal NbOH protons or Bronsted acidic protons associated with
FfA are potential biofuel components, industrial solvents, and key SiONb bridges may be responsible for the enhanced substrate
feedstocks [155157]. Furfural produced from pentosan-rich biomass conversion, but lead to the occurrence of side reactions (e.g., con-
by xylose cyclodehydration seems to proceed through a sequence densation) to lower the selectivity of product [164]. Microporous
of cascade reactions involving Lewis acid-catalyzed isomerization AM-11 crystalline niobium silicate prepared from a gel with molar
of xylose to xylulose and Bronsted acid-catalyzed dehydration of compositions of 11.5Na2O:8.2SiO2:Nb2O5:418.6H2O gives a xylose
xylulose to furfural (Fig. 9) [159,160]. In a non-enzymatic route for conversion of 90% and a signicantly increased furfural yield of 50%
xylose isomerization with the presence of a single Lewis acid cat- under identical reaction conditions (Table 2, Entry 6) [164]. The
alyst Sn-Beta zeolite in an aqueous solution, xylulose and lyxose are microporous AM-11 catalyst is more active than HY zeolite (39% yield
the primary and secondary products, respectively [158]. At ~60% at 94% conversion) and mordenite (28% yield at 79% conversion).
xylose conversion, a maximum xylulose yield of 27% with an 11% Appropriate concentration of niobium species (Si/Nb molar ratio:
yield to lyxose is attained at 100 C in 15 min. Analysis shows that 2.3/1) is important to x the distribution of Lewis-Bronsted acid sites
xylulose was thermodynamically and kinetically favored over lyxose (molar ratio: ~1/2-3) to obtain high furfural yields. Impregnation,
[161]. Thus, Bronsted-acid-catalyzed dehydration of xylulose to fur- rather than incorporation of niobium into the siliceous network of
fural is faster than that of xylose to furfural, and the combined use MCM-41 materials, is another effective method for the dehydra-
of Sn-Beta with a Bronsted acid catalyst (HCl or Amberlyst-15) can tion of xylose to furfural (Table 2, Entry 7), for which a signicant
produce furfural from xylose in a single pot at temperatures (~110 C) increase in the furfural yield from 37 to 60% is obtained in the
that are typically lower than those required for this reaction [158]. absence and presence of 0.5 gNaClgaq.sol.1 (0.5 g NaCl per gram aqueous
A furfural yield of ~38% is obtained using a combination of Lewis solution) when using MCM-Nb16 catalyst with nominal 16 wt% of
(CrCl3) and Bronsted (HCl) acids compared with ~29% using HCl alone Nb2O5 [165]. The combination of the highly distorted NbO6 octa-
at moderate temperatures (145 C) in a single aqueous phase, and hedra sites corresponding to Lewis acidic sites with the slightly
a 76% yield of furfural is obtained with the same combination of distorted surface NbO6, NbO7 and NbO8 sites associated with Bronsted
catalysts in a biphasic system using toluene as extractant (Table 2, acidic sites on MCM-41 [191], as well as the promoting effect of Cl
Entries 13) [162]. ions might be the reason for the superior results (Table 2, Entry 7).
Among the various supports (i.e., commercial fumed silica, -Al2O3,
2.2.1. Molecular sieves MCM-41, and SBA-15 silica) those with different amounts of Nb2O5
The isomerization of xylose to xylulose allows formation of fur- (4, 12 and 20 wt%), the Al12Nb catalyst with -Al2O3 support ap-
fural by facilitating the process of dehydration. Lewis acid sites parently promotes secondary reactions, as compared with silica
promote xylose isomerization, but lower furfural selectivity by cata- supported catalysts, while SBA12Nb and MCM12Nb bearing both
lyzing side reactions between xylose and furfural to form humins Bronsted and Lewis acid sites as well as micro-mesoporous struc-
(insoluble degradation products) [181,182]. Bronsted acids such as ture provide high xylose dehydration rates compared with
H2SO4, Amberlyst-15, MCMSO3H, and SBA-15SO3H protonate the commercial silica. A xylose conversion of 84% and furfural selec-
hydroxyl groups on the xylose to promote furfural formation tivity of 93% in water/toluene can be obtained with the SBA12Nb
[183188], but at a lower rate than Lewis acids [189,190]. To design catalyst (Table 2, Entry 8) [166].
ecient aqueous-phase dehydration catalysts, it is necessary to have To modify the Lewis and Bronsted acid functionality and mor-
an appropriate distribution of Bronsted to Lewis acid sites (Table 2). phological structure of zeolites, dealumination, desilication, and
As an example, MCM-41 (Table 2, Entry 4) provides furfural in 44% incorporation of other species have been used and the resulting ma-
yield from xylose (97% conversion) at 170 C after 3 h in n-BuOH/ terials are effective for the isomerization of xylose and subsequent
H2O (3:2, v/v) solvent probably due to its high specic surface area dehydration to yield furfural [192194]. Under batch conditions,
(800 m2/g), good adsorption capacity (average pore diameter = 3 nm), HMCM-22 zeolite and its delaminated counterpart (ITQ-2),
Table 2
BronstedLewis acid bifunctional solid catalysts used in the conversion of carbohydrate substrates into furfural with summary of reaction conditions, maximum catalytic activity, catalyst reuse and catalyst preparation method.

Entry Substrate Catalysta Reaction condition Catalytic activity Reusability Catalyst preparation Ref.

Solvent Temp Time Conv Yield Cycles Yieldb Method Calcination Waste

H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194


1 Xylose (1 wt%) 0.1 M HCl H2O 145 C 300 min 29% No Acid [162]
2 Xylose (1 wt%) 0.1 M HCl + 6 mM CrCl3 H2O 145 C 90 min 38% No Acid/Cr3+ [162]
3 Xylose (1 wt%) 0.1 M HCl + 6 mM CrCl3 H2O 140 C 120 min 96% 76% No Acid/Cr3+ [162]
4 Xylose (15 wt%) 66.7 wt% acidic MCM-41 n-BuOH/H2O (3:2, v/v) 170 C 3h 97% 44% Activation 560 C, 6 h NMc [163]
5 Xylose (10 wt%) 100 wt% Nb/MCM-41 Toluene/H2O (7:3, v/v) 160 C 6h 99% 39% 3 34% Sol-gel 400 C, 4 h NM [164]
6 Xylose (10 wt%) 100 wt% AM-11 niobium silicate Toluene/H2O (7:3, v/v) 160 C 6h 90% 50% 3 43% Sol-gel 400 C, 4 h NM [164]
7 Xylose (10 wt%) 33.3 wt% Nb2O5/MCM-41 Toluene/H2O -NaCl (7:5, v/v) 170 C 3h ~98% 60% 3 ~56% Impregnation 550 C, 6 h NM [165]
8 Xylose (20 g/L) 20 wt% SBA12Nb Toluene/H2O (1:1, v/v) 160 C 24 h 84% 93% Impregnation 550 C, 6 h NM [166]
9 Xylose (3 wt%) 66.7 wt% HMCM-22 (Si/Al: 24) Toluene/H2O (7:3, v/v) 170 C 16 h 98% 71% 4 ~60% Sol-gel, ion-exchange 540 C, 6 h NM [167]
zeolite
10 Xylose (10 wt%) 66.7 wt% Beta/TUD-1 Toluene/H2O (7:3, v/v) 170 C 8h 98% 74% 4 ~69% Sol-gel 600 C, 10 h NM [168]
11 Xylose (10 wt%) del-Nu-6(1) Toluene/H2O (7:3, v/v) 170 C 4h 90% 47% 3 ~45% Swelling ultrasonication 580 C, 7 h NM [169]
12 Glucose (0.5 wt%) H-Beta GVL-H2O (9:1 , v/v) 175 C 40 min 99% 37% Activation 450 C, 6 h NM [170]
13 Xylose (10 wt%) 66.7 wt% SAPO-11 Toluene/H2O (7:3, v/v) 175 C 4h 69% 38% 3 ~42% Sol-gel 550 C, 6 h NM [171]
silicoaluminophosphate
14 Hemicellulose (1 wt%) 25 wt% SAPO-44 Toluene/H2O (1:1, v/v) 170 C 8h 63% 8 64% Sol-gel 550 C, 6 h NM [172]
15 Hemicellulose (1 wt%) 25 wt% SAPO-11 Toluene/H2O (1:1, v/v) 170 C 8h 35% Sol-gel 550 C, 6 h NM [172]
16 Xylose (10 wt%) 66.7 wt% eHTiNbO5MgO Toluene/H2O (7:3, v/v) 160 C 4h 92% 55% 3 ~35% Exfoliation No NM [173]
17 Xylose (10 wt%) 100 wt% TiO2ZrO2 H2O 250 C 5 min 80% ~35% Precipitation 600 C, 6 h NM [174]
18 Xylose (10 wt%) 66.7 wt% SO4/ZrO2Al2O3 Toluene/H2O (7:3, v/v) 160 C 4h >90% 50% 3 ~40% Impregnation 650 C, 5 h NM [175]
19 Corncob (10 wt%) 20 wt% SO4/TiO2ZrO2/La3+ H2O 180 C 2h 7% Precipitation, impregnation 550 C, 4 h NM [176]
20 Xylose (10 wt%) 66.7 wt% ZrAlW-MP Toluene/H2O (7:3, v/v) 170 C 4h 98% 51% 4 ~42% Precipitation 630 C, 5 h NM [177]
21 Xylose (10 wt%) 66.7 wt% (VO)2P2O7 Toluene/H2O (7:3, v/v) 170 C 4h 91% 53% 4 ~50% Evaporation 550 C, 2 h NM [178]
22 Xylose (10 wt%) 66.7 wt% SO4/ZrO2Al2O3/SBA-15 Toluene/H2O (7:3, v/v) 160 C 4h 99% 53% 3 39% Impregnation 650 C, 3 h NM [179]
23 Xylose (20 wt%) 20 wt% MgF2PF Toluene/H2O (1:1, v/v) 160 C 20 h 79% 71% Sol-gel, post-grafting No NM [180]
a
Catalyst dosage relative to the substrate.
b
The yield of furfural in the last cycle.
c NM: not mentioned. TUD-1: a siliceous mesoporous matrix, del-Nu-6(1): a delaminated zeolite, SAPO-11: silicoaluminophosphate, ZrAlW-MP: mixed zirconium tungsten oxides impregnated with aluminum on mesophases

(MP) of zirconia, MgF2-PF: MgF2 prepared from Mg and peruorosulfonic (PF) precursor.

111
112 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

furfural yields of up to 71% and 54% are obtained at more than 96% scale, development of robust and stable Bronsted/Lewis acid
xylose conversion with a water/toluene (3/7, v/v) and a water solvent bifunctionalized solid zeolite-like materials is urgently needed.
system, respectively (Table 2, Entry 9) [167]. A decrease in the Si/
Al ratio from 38 to 24 for HMCM-22 increases the total amount 2.3. Synthesis of levulinic acid or levulinate esters
of Lewis plus Bronsted acid sites and improves catalytic perfor-
mance without signicantly affecting furfural selectivity. With the Reactions producing LA and levulinate esters (LEs) from sugar
same Si/Al molar ratio of 24, the ITQ-2 catalyst exhibits compara- molecules represent important pathways for the transformation of
ble catalytic activity to its counterpart HMCM-22 and correlates biomass to chemicals and biofuels [200202]. LEs such as methyl
with the like total amounts of Lewis and Bronsted acid sites of these levulinate (ML) and ethyl levulinate (EL) have numerous potential
materials. The structure of the catalysts can be regenerated by applications in the fragrance and avoring industry and can be used
thermal treatment to remove organic residues, and furfural yields as additives for diesel and biodiesel transportation fuels [203206],
in consecutive uses remain approximately constant [167]. In a similar as well as preferred substrates for chemical conversion to many other
manner, a composite material consisting of commercial nano- products [207].
crystalline zeolite Beta (Si/Al: 12) in the protonic form incorporat- Under relatively harsh conditions (ca. 200 C) at low sulfuric acid
ed in a purely siliceous TUD-1 mesoporous matrix (denoted Beta/ concentrations (0.01 mol L1) in methanol solvent, glucose can be
TUD-1) is an effective catalyst for the acid-catalyzed conversion of rapidly (ca. 10 min) and almost quantitatively converted into a key
xylose into furfural and gives a higher furfural yield than bulk Beta and stable intermediate product methyl glucoside, which when
(74% vs 54%) at xylose conversions of 98% in H2O/toluene (3/7, v/v) allowed to react to completion (150 min) provides methyl levulinate
(Table 2, Entry 10) [168]. Delaminated zeolite del-Nu-6(1) with Si/ in yields of 50% (Table 3, Entry 1) [228]. The formation of LA and
Al: 29, obtained by swelling and ultrasonication of a laminar LEs (2465% yields) from glucose or cellulose can be obtained with
precursor of Nu-6(2) (i.e., Nu-6(1) with Si/Al: 38) [195], which has other SO3H mono-functionalized homogeneous and heteroge-
a specic surface area about seven times higher than that for proton- neous materials [e.g., SO3HSBA-15, sulfonated chloromethyl
exchanged Nu-6(2), promotes the reaction to have a rate of about polystyrene, 1-(1-propylsulfonic)-3-methylimidazolium chloride
two times higher than that for HNu-6(2), affording a relatively fur- ([PSMI]Cl), and [C4H6N2(CH2)3SO3H]3nHnPW12O40 (n: 1, 2 and 3; HPA
fural yield of 47% in a watertoluene (3/7, v/v) biphasic reactor ILs)] in various reaction systems (Table 3, Entries 25) [208211].
system (Table 2, Entry 11), compared with 34% in the presence of Relatively long reaction times and high temperatures are general-
an H-mordenite sample with Si/Al of ~6 [169]. The yield of furfu- ly required for high yields of LA and LEs, otherwise alkyl
ral from C6 sugar was low with Bronsted acids such as mineral acids glucopyranosides are likely to be the major products in alcohols at
(H2SO4 and HCl) and A70 (with SO3H), Lewis acids (-Al2O3), and low temperatures (<140 C) [211].
combined Bronsted and Lewis acids (a mixture of -Al2O3 and A70);
whereas the furfural yield was signicant when zeolites (H- 2.3.1. Molecular sieves
mordenite and H-Beta) were used, and yields of furfural (>30%) The combination of Lewis and Bronsted acids has a strong syn-
could be produced from glucose by cascade dehydration and ergistic effect on catalytic activity for the direct decomposition of
decarbonylation using GVL as the solvent (Table 2, Entry 12) [170]. glucose to LA [229231] as shown in Table 3. With respect to the
Both C6 and C5 sugars have the potential to be converted into fur- CrCl3H3PO4 mixed acids, catalytic systems with a CrCl3/H3PO4 ratio
fural with zeolite catalysts. of 0.40.5 show superior reactivity (Table 3, Entries 68) [212].
Bronsted acids can increase the H+ concentration, facilitating the
2.2.2. Metal oxides Lewis acidmediated glucose-to-fructose isomerization thus en-
Despite the advantages of zeolites, many forms are not stable hancing selectivity [232]. In the subsequent dehydration reaction,
in aqueous solutions under hydrothermal conditions (ca. ~150 C) CrCl3 and H2PO4/HPO42 combine with 2,5-dioxohex-3-enal to form
[196,197] so that their use requires careful consideration of the re- a complex, promoting the decomposition of the intermediates like
action system. Silicoaluminophosphate catalysts (SAPO) containing HMF to LA. In this scenario, zeolites and mesoporous materials offer
bifunctional Lewis and Bronsted properties are found to have good ecient conversion routes from crude biomass due to their high
stability under hydrothermal conditions (Table 2, Entry 13) [171], concentration of active sites, high thermal/hydrothermal stability
of which SAPO-44 with a Si/P ratio of 44 gives 63% furfural yields and enhanced shape selectivity (i.e., the selective accessibility of re-
for a one-pot conversion with hemicellulose substrate and has con- actant, intermediate, or product to zeolite pores) [233]. In general,
stant activity for multiple cycles (Table 2, Entry 14) [172]. The aluminum-free Lewis acidic zeotype materials and mesoporous mo-
catalytic performance of SAPO-11 with a Lewis/Bronsted acid ratio lecular sieves containing Sn, Ti, or Zr are able to isomerize hexoses,
of 0.48 (total acid content: 111 mol/g) is superior to its counter- pentoses and trioses, and convert them into desirable chemicals
part SAPO-44 with a ratio of 1.3 (total acid content: 119 mol/g) [234238]. Saravanamurugan and Riisager [213] show that glucose
in xylose-to-furfural conversions (35% furfural yield; Table 2, Entries eciently isomerizes glucose to form fructose in alcoholic media
14 and 15), indicating the importance of the distribution of Bronsted over zeolites such as HY(2.6), HUSY(6), HUSY(30), H(12.5), H(19)
and Lewis acid sites [171]. Metal oxidebased BronstedLewis acid and HZSM(15) without auxiliary Lewis acid metals (e.g. Sn, Ti and
bifunctional solid catalysts such as exfoliated titanate, niobate and Zr) other than Al. As compared with other zeolites, HUSY(6) con-
titanoniobate nanosheets (Table 2, Entry 16) [173], mixed-oxide taining more Lewis acid sites [239] as well as a certain amount of
TiO2ZrO2 (Table 2, Entry 17) [174], sulfated zirconia/titania (Table 2, Bronsted acid sites facilitate the isomerization of (methylated)
Entries 18 and 19) [175,176], tintungsten mixed oxide [198], and glucose to fructose and the succeeding dehydration and rehydra-
Zr(W,Al) mixed oxides (Table 2, Entry 20) [177] are effective solid tion to ML in methanol provides relatively high yields (ca. 50%)
catalysts in the aqueous-phase dehydration of xylose to furfural. Nev- (Table 3, Entry 9).
ertheless, active water soluble species leach metal oxides and affect Metal halides, especially chromium chloride, facilitate mutaro-
the dehydration activity of these catalysts (Table 2, Entry 21) tation and isomerization of glucose to fructose with simultaneous
[178,199]. Regeneration of the catalysts can be realized by the dehydration to HMF, and the subsequent rehydration with hydro-
removal of residual species through the use of H2O2 as oxidant or nium ions affords LA [240,241]. An alternative method is to modify
calcinations at certain temperatures (Table 2, Entries 22 and 23) the HY zeolite structure by combining the zeolite and metal halide
[179,180]. To meet the specications of a clean, renewable, and eco- (CrCl3) to form a hybrid catalyst for improving the catalytic prop-
nomical facility for producing furfural from sugars on the industrial erties and enhancing LA yields [214]. The catalytic reaction of the
Table 3
BronstedLewis acid bifunctional solid catalysts used in the conversion of carbohydrate or furfuryl alcohol substrates into levulinic acid or its esters with summary of reaction conditions, maximum catalytic activity, catalyst
reusability and catalyst preparation method.

Entry Substrate Catalysta Reaction condition Product Catalytic activity Reusability Catalyst preparation Ref.

Solvent Temp Time Conv Yield Cycles Yieldb Method Calcination Waste

1 Glucose (5.4 wt%) 0.01 mol/L H2SO4 MeOH 200 C 2.5 h ML 100% 50% Acid [208]
2 Cellulose (21.0 wt%) 33 wt% [PSMI]Cl 54 wt% H2O/EtOH 150 C 48 h LA 100% 24% Condensation + acidication NM [208]
3 Cellulose (20.0 wt%) 200 wt% HPA ILs 10 wt% H2O/MIBK 140 C 12 h LA 100% 63% 6 60% Condensation + acidication NM [209]
4 Cellulose (5 wt%) 300 wt% CPSO3H 10 wt% H2O/GVL 170 C 10 h LA 100% 65% 3 43% Sulfonation NM [210]
5 Cellulose (2.8 wt%) SO3HSBA-15 (7.1%) EtOH 140 C 24 h EDGP 94% 80% (0) NM [211]
(EL)

H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194


6 Glucose (1.0 wt%) 72 mol% CrCl3 H2O 170 C 4.5 h LA 100% 10% Cr3+ [212]
7 Glucose (1.0 wt%) 72 mol% H3PO4 H2O 170 C 4.5 h LA 37% 8% Acid [212]
8 Glucose (1.0 wt%) 36 mol% CrCl3H3PO4 H2O 170 C 4.5 h LA 100% 50% Acid, Cr3+ [212]
9 Glucose (2.5 wt%) 60 wt% HUSY(6) MeOH 160 C 20 h ML 50% 5 45% Activation 550 C, 6 h NMc [213]
10 Glucose (1.0 wt%) 100 wt% Cr/HY(15) (1:1, w/w) H2O 160 C 3h LA 100% 62% Impregnation 400 C, 24 h NM [214]
11 Glucose (2.0 wt%) 100 wt% Fe/HY(2.5) (10 wt% H2O 180 C 3h LA 100% 62% 5 47% Impregnation 400 C, 5 h NM [215]
Fe loading)
12 Cellulose (5.0 wt%) Fe/HY(2.5) (10 wt% Fe loading) [BMIM]Br 120 C 3h TRS 61% 5 46% Impregnation 500 C, 5 h NM [216]
13 FfA (2.9 wt%) 34 wt% AlTUD-1 EtOH 140 C 24 h EL 100% 80% NM [217]
14 FfA (2.9 wt%) 34 wt% Beta/TUD-1 EtOH 140 C 24 h EL 100% 63% NM [217]
15 FfA (2.9 wt%) 34 wt% H-Beta EtOH 140 C 24 h EL 100% 60% NM [217]
16 FfA (2.9 wt%) 34 wt% ITQ-2 EtOH 140 C 24 h EL 100% 60% Delamination NM [217]
17 FfA (2.9 wt%) 34 wt% HMCM-22 EtOH 140 C 24 h EL 100% 47% NM [217]
18 Glucose (15.0 wt%) 20wt% Ru/HZSM-5 H2O 200 C 1h LA 86% 38% Impregnation 500 C, 4 h NM [218]
19 Glucose (15.0 wt%) 20wt% Ru/AlSBA-15 H2O 200 C 1h LA 85% 29% Impregnation 500 C, 4 h NM [218]
20 Glucose (15.0 wt%) 10wt% Ru/AlSBA-15 H2O 200 C 1h LA 85% 28% Impregnation 500 C, 4 h NM [218]
21 Glucose (15.0 wt%) 10wt% Ni/AlSBA-15 H2O 200 C 1h LA 91% 29% Impregnation 500 C, 4 h NM [218]
22 Starch (10 wt%) 20wt% Ru/HZSM-5 H2O 200 C 1h LA 81% 25% Impregnation 500 C, 4 h NM [218]
23 Starch (10 wt% 20wt% Ru/AlSBA-15 H2O 200 C 1h LA 82% 32% Impregnation 500 C, 4 h NM [218]
24 Cellulose (1.25 wt%) 60% H-resin 5 wt% NaClH2O 200 C 5h LA 97% 20% Ion-exchange No NM [219]
25 Cellulose (1.25 wt%) 60% Fe/H-resin 5 wt% NaClH2O 200 C 5h LA 91% 33% Impregnation No NM [219]
26 Glucose (15 wt%) 1.7 wt% GOSO3H (Lewis type S:O) H2O 200 C 2h LA 89% 79% 5 45% Post-grafting No NM [220]
27 Glucose (5.0 wt%) 2.5 wt% SO4/ZrO2 EtOH 200 C 3h EL 98% 30% 5 27% Precipitation, impregnation 550 C, 3 h NM [221]
28 Sucrose (5.0 wt%) 2.5 wt% SO4/TiO2 MeOH 200 C 2h ML 43% Precipitation, impregnation 550 C, 3 h NM [222]
29 Glucose (5.0 wt%) 2.5 wt% SO4/TiO2 MeOH 200 C 2h ML 33% 5 20% Precipitation, impregnation 550 C, 3 h NM [222]
30 Glucose (5.6 wt%) 50 wt% SO4/ZrO2/SBA-15 MeOH 140 C 24 h ML 25% Post-grafting, impregnation 550 C, 3 h NM [223]
31 Glucose (3.9 wt%) 50 wt% SO4/ZrO2/SBA-15 EtOH 140 C 24 h EL 24% 3 25% Post-grafting, impregnation 550 C, 3 h NM [223]
32 Rice straw (6.7 wt%) 13.3 wt% S2O8/ZrO2SiO2Sm2O3 H2O 200 C 10 min LA 70% 3 67% Precipitation 110 C, 12 h NM [224]
33 Cellulose (2 wt%) 100 wt% ZrO2 H2O 180 C 3h LA 100% 54% 5 55% No NM [225]
34 Cellobiose (12.5 wt%) 5 mol% [PyBS]5PV2Mo10O40 H2O 150 C 3h LA 100% 46% 4 45% Hybridization No NM [226]
35 Cellulose (10 wt%) 50 wt% ZrO2 H2O 240 C 20 min LA 87% 52% 5 40% Activation 250 C, 1 h NM [227]
a Catalyst dosage relative to the substrate.
b Yield of LA or esters in the last cycle.
c
NM: not mentioned.
LA: levulinic acid, ML: methyl levulinate, EL: ethyl levulinate, MeOH: methanol, EtOH: ethanol, [PSMI]Cl: 1-(1-propylsulfonic)-3-methylimidazolium chloride, HPA ILs: [C4H6N2(CH2)3SO3H]3-nHnPW12O40 (n: 1, 2 and 3), MIBK:
methyl isobutyl ketone, CP-SO3H: sulfonated chloromethyl polystyrene, GVL: -valerolactone, EDGP: ethyl-d-glucopyranoside, HY/HUSY: Y type zeolites, [BMIM]Br: 1-butyl-3-methylimidazolium bromide, TRS: total reducing
sugars, FfA: furfuryl alcohol, GO: graphene oxide, PyBS: a zwitter-ion prepared from pyridine and 1,4-butane sulfone.

113
114 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

hybrid catalysts is predominantly inuenced by the type of acid sites Graphene oxide (GO)-based solid catalysts with SO3H functional
(Lewis acidity enhanced by Cr3+), amount of acid sites and strength groups (GOSO3H) are ecient for the selective decomposition of
surface area, hierarchical porous structures and shape selectivity so glucose into LA giving a yield of 78% for glucose conversions of 89%
that high LA yields (ca. 62%) are achieved with the 1:1 weight ratio (Table 3, Entry 26) [220]. Lewis acid sites caused by the electron in-
of CrCl3 and HY (Table 3, Entry 10). A series of Fe/HY zeolite cata- ductive effect of the S=O double bonds in the surface sulfate complex
lysts was composed of HY zeolite and FeCl 3 prepared by wet [249], together with the presence of other functional groups such
impregnation method exhibit high acid site density and increased as carboxyl and hydroxyl play positive roles in enhancing the isom-
number of Lewis acid sites, in which Fe/HY catalyst with 10% Fe erization and adsorption of glucose for the reaction. The layered
loading provides high catalytic performance with 62% LA yields being morphology of GOSO3H allows rapid diffusion of the reactants and
obtained from glucose (Table 3, Entry 11) [215] with a total reduc- products, and the SO3H groups are thermally stable and do not cause
ing sugar (TRS) yield of 61% being obtained from cellulose in leaching into the reaction mixture. Introduction of Bronsted acid
[BMIM]Br (Table 3, Entry 12) [216]. Those authors [215] show that sites such as phosphate [250,251], sulfate [221223], and superacid
Lewis acid sites promote isomerization of glucose into fructose and groups [224] into metal oxides (e.g., ZrO2, SnO2 and TiO2) bearing
that the combination of Bronsted and Lewis acidity favors the Lewis acid or Lewis base sites responsible for glucose-to-fructose
dehydration/rehydration reaction, while the increase in the number isomerization [225] gives moderate to good catalytic performance
of Lewis acid sites might also decrease the yields of LA by promot- for sugar-to-LA/LE transformations (Table 3, Entries 2733).
ing the decomposition of glucose and reaction between glucose and To identify the dominant reaction routes for the synthesis of LA
furfural to form humins. LA can also be synthesized from xylose con- from sugars, Yang et al. [252] studied acid-mediated conversion of
version involving an intermediate hydrogenation of furfural to FfA glucose and fructose in aqueous solutions with density functional
assisted by co-produced formic acid under hot-compressed water theory (DFT). The dehydration of fructose catalyzed by a Bronsted
[242]. acid catalyst is preferential for protonating O2H hydroxyl group,
Zeolites commonly encounter drawbacks associated with their thus there are a number of potential reaction paths to HMF. The
microporosity including limited accessibility of active sites to the succedent rehydration of HMF to give LA is dicult and competes
substrate and the existence of strong internal diffusion limitations with polymerization or condensation processes that result in the
in the liquid-phase conversion of biomass or biomass-related chemi- formation of humins. When glucose is the reactant, the O1H group
cals. Aluminosilicate catalysts with improved texture properties have is the preferred protonation site. In this case, HMF is unable to be
been achieved through: (1) use of an organic template for intro- formed in the relevant reaction paths, which leads to humin pre-
ducing mesopores and obtaining relatively narrow pore-size cursors and reversion products. However, in the DFT simulations,
distributions [243245], (2) reducing the crystallite sizes of zeo- LA can be produced from glucose through a reaction mechanism
lites to the nano-scale and embedding nanocrystalline zeolites into possibly without forming fructose and HMF intermediates, since pro-
mesoporous silica matrices [246], and (3) delaminating lamellar pre- tonation of other sites including O2H, O3H and O5 positions
cursors of zeolites [247,248]. Neves et al. [217] found that several is able to activate glucose at a lower rate. Nevertheless, these sim-
aluminosilicates including mesoporous Al-TUD-1, composite Beta/ ulation results are in contradiction with the known reaction pathway
TUD-1 and nanocrystalline zeolite H-Beta, as well as ITQ-2 and the to some extent, since fructose and HMF are key intermediates for
zeolite counterpart H-MCM-22 are active to transform FfA into EL LA formation from sugars containing glucose units. Hence, an al-
in ethanol solvent (Table 3, Entries 1317). Among these catalysts ternate route can be hypothesized for sugar-to-LA transformation,
(Table 3, Entries 1317), Al-TUD-1 gives high EL yields (ca. 80%) in which ve-membered ring carbocations are initially generated
despite its relatively weak acidity that is essentially of the Lewis by direct activation of the O1H, O2H, O3H and O5 sites, fol-
type, which might be attributed to its high specic surface area that lowed by a sequence of acid-catalyzed isomerization reactions to
enhances active site accessibility along with its inhibition of by- some specic intermediates that are dependent on catalytic systems
products. SBA-15 incorporated with Al by the post-synthesis method and that ultimately lead to LA by decarboxylation.
with a nominal Si/Al molar ratio of 30:1 and the Ni- or Ru-doped Li et al. [226] reported one-pot transformation of cellobiose into
AlSBA-15 and ZSM-5 catalysts prepared by wetness impregna- LA and formic acid via an aqueous phase partial oxidation (APPO)
tion have characteristic properties of mesoporous materials (9.23 nm) process illustrated in Fig. 10, wherein both the Bronsted-acidic sites
and an increased acidity (SBA-15: 0.23 mmol/g < AlSBA-15: in the IL cations and the redox catalytic sites in the polyoxometalate
0.45 mmol/g < 10 wt% Ni/AlSBA-15: 0.53 mmol/g < 10 wt% Ru/ (POM) anions of [PyBS]5PV2Mo10O40 catalyst are involved. At an oxygen
AlSBA-15: 0.64 mmol/g < 20 wt% Ru/AlSBA-15: 0.81 mmol/g; partial pressure of 3 MPa, 100% cellobiose conversion with 46% se-
ZSM-5: 0.51 mmol/g < 20 wt% Ru/ZSM-5: 0.70 mmol/g) [218]. The lectivity to LA and 26% selectivity to formic acid is obtained (Table 3,
moderate increase of Ru amount in ZSM-5 and Al-SBA-15 cata- Entry 34). The prepared [PyBS]5PV2Mo10O40 is remarkably stable and
lysts increases the levels of LA, and provides LA selectivities as high gives LA selectivities of about 45% for multiple uses. Examination of
as 44% for glucose for a 20 wt% Ru/ZSM-5 catalyst (Table 3, Entries the spent catalyst with 51V NMR spectroscopy of the spent catalyst
1821) [218]. The acid content and porous properties proved to be did not reveal any evidence of impurities or degradation. In con-
important keys to control yield and selectivity of LA, wherein the trast, the simple catalytic material ZrO2 provides LA yields of 52%
MFI structure of ZSM-5 is suitable for glucose monosaccharide through catalytic partial oxidation of cellulose in aqueous media under
hydrothermolysis while the hexagonal mesoporous structure of lean air pressure of 2.4 MPa with 2.8% O2 at 240 C in 20 min (Table 3,
AlSBA-15 is preferable for hydrothermolysis of starch polysac- Entry 35) [227]. In this catalytic process, gluconic acid rather than
charide (Table 3, Entries 18, 19, 22 and 23). HMF is the key intermediate to produce LA (Fig. 10), thus this shows
the importance of redox over acidbase properties for the ZrO2 cata-
2.3.2. Resins and oxides lyzed oxidative deconstruction of cellulose. Recycle of the ZrO2 catalyst
For polymer based acid ion-exchange resins with Bronsted acid, gave yields of LA that slightly decreased from ~50% to ~40% over ve
the incorporation of Lewis acid sites enhances their reactivity for uses, for which the ZrO2 catalyst was only regenerated once by facile
carbohydrate-to-LA transformations. Fe-resin prepared by modi- calcination at 250 C after the rst cycle.
cation of Dowex 50 with Fe3+ through cation exchange shows both It can be deduced that the isomerization of glucose into fruc-
Bronsted and Lewis acidity, and gives 91% conversion of cellulose tose promoted by Lewis acid sites is a key step for transforming
and ~80% total selectivity of glucose (39% yield) and LA (33% yield) glucose units into LA or its esters and the hydrolysis/dehydration/
in 5 wt% NaCl aqueous solution (Table 3, Entries 24 and 25) [219]. rehydration reactions are favorable with combination of Bronsted
H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194 115

Fig. 10. Pathways for the transformation of cellulose/cellobiose into levulinic acid (LA) and formic acid via an aqueous phase partial oxidation (APPO) process. Adapted
with permission from Refs. 226 and 227, Copyright 2014 Wiley-VCH; Copyright 2012 Royal Society of Chemistry.

and Lewis acid sites. Nevertheless, the increase in Lewis acidity may Y-zeolite and silicaalumina, HZSM-5 (Si/Al: 600) has superior ar-
also decrease the yield of LA or its esters by promoting nonselec- omatic yields and gives the least amount of coke with more than
tive decomposition of glucose units and the reactions among 30 molar carbon% of aromatics being obtained from glucose, xylitol,
substrates, intermediates (e.g., fructose and HMF) and products to cellobiose, and cellulose at a reaction temperature of 600 C and a
form soluble polymers and humins [253]. The integration of acidic reaction time of 240 s [258]. In pyrolysis, HZSM-5 zeolites with high
sites with redox properties allow catalysis of the partial oxidation silica-to-alumina ratios, which correlate with a large separation of
of glucose or cellulose to gluconic acid other than HMF, followed acid sites, are effective for eliminating methoxyl groups, cleaving
by decarboxylation to yield LA. Therefore, the development of func- ether and aliphatic CC bonds, and dehydrating aliphatic hy-
tional catalytic materials containing acidic sites appropriately droxyl groups [259]. Bronsted acid sites have a critical role in the
combined with other active species that can promote different re- upgrading reactions in consideration of HZSM-5 more active than
action pathways shows great potential for ecient valorization of silicalite-1 [260,261]. Lewis acid sites play an important role in hy-
biomass to LA and other biorenery products. drogen atom transfer that is a major factor in aromatization
[262,263]. For example, Zn-doped HZSM-5 improves furan conver-
2.4. Other methods and products sion (100% vs. 80%), yielding more benzene (72% vs. 29%), carbon
oxides (6% vs. 3%), and alkenes (>6% vs. ~6%) than native HZSM-5
2.4.1. Catalytic fast pyrolysis (CFP) for coke catalyst at 500 C within 13 min [264]. H-atom transfer activity, pos-
The ideal process for conversion of solid biomass into liquid fuels sibly correlated to the Lewis acid sites offered by exchanged Zn
would be one that could occur in a single step at short reaction times. cations, is important for high aromatic yields, and probably sup-
Catalytic fast pyrolysis (CFP) is a promising candidate for convert- presses the alkylation of benzene to toluene. Cheng et al. [265]
ing oxygenated compounds generated from pyrolysis into gasoline report that Ga-promoted HZSM-5 catalysts increase the yield of
range aromatics in the presence of a zeolite catalyst (Fig. 11) aromatics through CFP process by 40% compared with that of stan-
[254257]. Among the various zeolites such as silicalite, Beta, dard HZSM-5 catalysts, in which Ga catalyzes both the desired
116 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

Fig. 11. Possible routes for catalytic fast pyrolysis (CFP) of glucose over a zeolite. Adapted with permission from Ref. 254, Copyright 2010 Elsevier.

decarbonylation reactions and olen aromatization, while the ZSM-5 2.4.2. Phthalic anhydride
portion of the catalyst promotes the remaining reactions such as As discussed above, furanic compounds (e.g., benzofuran) gen-
oligomerization and cracking to produce aromatics. erated in HZSM-5 nanopores are important intermediates in
The micropore openings in ZSM-5 used in that study had a size producing aromatic-range biofuels [275,276]. In the CFP of biomass,
in the range of 5.25.9 which is close to the optimum required a DielsAldol reaction followed by a ring-opening process involv-
for conversion of glucose toward aromatic species [266]. It was ing dehydration reaction has been reported as the key reaction
shown that the aromatic yield was a function of the pore size of pathway [277]. Lewis acidity is more effective than Bronsted acidity
the zeolite catalyst, that is, the majority of aromatics and oxygen- at catalyzing DielsAlder cycloaddition among different types of acid
ated species present during reaction are accessible to the pores of catalysts [278,279]. The WOxZrO2 and zeolite-based catalysts such
most medium and large-pore zeolites but are excluded from en- as HY, H and Sn bearing both Bronsted and Lewis acid sites,
tering small pores. Desilication of HZSM-5 zeolite with 0.5 M NaOH however, are active for conversion of biomass-derived furans to aro-
solution creates intraparticle mesopores in the microporous zeolite, matics under relatively mild conditions (around 200 C) [280283].
producing more aromatic hydrocarbons (carbon yields of 2630%) This dehydration process is inherently dicult, because the formed
and less coke (4041%) in CFP of beech wood than the parent intermediates are sensitive to heat and readily undergo retro-Diels
microporous HZSM-5 (23% aromatics and 44% coke) [267]. Acid Alder reaction [284]. For this issue, mixed sulfonic carboxylic
dealuminated HZSM-5 (leaching agent of H3PO4, H+ concentration anhydrides used as strong acylating agents rapidly cleave the ether
of 2 mol/L, temperature of 20 C, and time of 4 h) decreases the coke rings with high selectivity to their ring-opened products [285], and
yield from 44% with original HZSM-5 to 27%, and affords in- an 80% selectivity to phthalic anhydride is obtained from biomass-
creased yields of target chemicals (14% olens and 32% aromatics) derived furan and MA after running the reaction for 2 h at 25 C to
compared with the original HZSM-5 catalyst (10% olens and 25% form a stable intermediate from the DielsAldol product assisted
aromatics) [268]. Zeolites with small pores severely hinder the dif- by acetyl methanesulfonate (Fig. 12), followed by dehydration at 80 C
fusion of both reactants and products and are unable to produce for 4 h to drive the reaction to completion [286].
aromatics from glucose, instead yielding a mixture of oxygenates,
CO, CO2 and coke, while zeolites with large pores allow for fast re- 2.4.3. 5-Ethoxymethylfurfural (EMF)
actant diffusion and lead not only to the formation of larger amounts The compound EMF, which has an energy density of 8.7 kW h L1,
of polyaromatics, but also to signicant coke formation [269]. Several is a promising second generation biofuel [287]. Generally, Bronsted
oxygenates such as HMF, furfural and guaiacol might also be formed acids catalyze HMF, fructose and fructose-based sugars to produce
in relatively high yields [270273], which would contribute to rapid EMF in high yields, but are inactive for glucose-to-EMF transfor-
coke formation and catalyst deactivation on HZSM-5 during pyrol- mation [288295]. To explore the possibility of directly converting
ysis oil upgrading [274]. glucose to EMF, Lew et al. [296] developed a catalytic system by
H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194 117

Fig. 12. Synthesis of phthalic anhydride from dehydration of a Diel-Aldol product 1 proceeding through a stable intermediate 2 by using mixed sulfonic carboxylic anhy-
drides as strong acylating agents. Adapted with permission from Ref. 286, Copyright 2014 Royal Society of Chemistry.

combining the Lewis acid zeolite Sn-Beta with Bronsted acid while the use of disaccharides and polysaccharides would entail an ad-
Amberlyst 131 in a single pot. In this catalytic system, the isom- ditional cleavage to glucose or fructose that could be promoted by
erization of glucose to fructose proceeds with zeolite Sn-Beta, and Bronsted and Lewis acids [303] before the retro-aldol cleavage (Fig. 14).
the resulting fructose is dehydrated to HMF followed by etheri- Various mechanisms have been proposed to explain the conversion of
cation to afford EMF using Amberlyst 131 (Fig. 13). After reacting GLY and DHA to alkyl lactates [305308]. In one reaction pathway, both
at 90 C for 24 h, an EMF yield of 31% is obtained from glucose in Lewis acids and weak Bronsted acids such as acetic acid catalyze se-
ethanol. EL is readily formed during synthesis of EMF from HMF and quential dehydration and rearrangement of GLY in equilibrium with
fructose in the presence of strong Bronsted acid catalysts at high DHA [309] into pyruvic aldehyde (PAL) [310,311], and the resulting PAL
temperatures [297299]. is further converted into the desired alkyl lactates in the presence of
a Lewis acid in alcoholic solvents, otherwise an undesirable acetal by-
2.4.4. Alkyl lactates product would be generated in a parallel reaction path under the action
In contrast, Lewis acids, especially Sn-Beta, might facilitate the direct of strong Bronsted acid groups (Fig. 14) [304]. A Lewis acid in combi-
conversion of hexoses such as glucose, fructose, and sucrose into alkyl nation with a weak Bronsted acid is not only effective for the formation
lactates [300302]. In the catalytic process of sugar-to-alkyl lactate con- of HMF and furfural [312314], but also plays an important role in
version, it is generally accepted that the conversion involves initial catalyzing glucose into fructose [315,316] and retro-aldol reaction of
isomerization of aldose into ketose, followed by retro-aldol to the cor- hexoses into trioses to facilitate the formation of alkyl lactates [317
responding trioses, glyceraldehyde (GLY) and dihydroxyacetone (DHA), 319].

Fig. 13. Combination of Sn-Beta and Amberlyst-15 for glucose-to-EMF (5-ethoxymethylfurfural) transformation involving HMF (5-hydroxymethylfurfural) as intermediate.
Adapted with permission from Ref. 296, Copyright 2012 American Chemical Society.
118 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

Fig. 14. Plausible pathway for converting sugars into alkyl lactates in alcoholic solvents. Adapted with permission from Ref. 304, Copyright 2012 American Chemical Society.

Acid catalysts are generally preferable for raw oils containing role of Lewis and Bronsted acid sites in the dehydration of glycer-
moisture and free fatty acids (FFAs) in the simultaneous esteri- ol on niobium oxide and Na+-exchanged niobium oxide using FT-
cation of FFAs and transesterication of triglycerides to produce IR (Fourier transform infrared spectroscopy) supported by DFT
biodiesel [320,321]. At a reaction temperature (ca. 200 C), esteri- calculations. It was found that Lewis acid sites activate primary CO
cation and transesterication steps can be both promoted by a bonds of glycerol to form 2-propene-1,2-diol, but Bronsted acid sites
Bronsted catalyst such as 12-tungstophosphoric acid [322,323]. In- are involved in the formation of acrolein. Wang et al. [333] dem-
troduction of Lewis acid sites into the catalytic process can lower onstrated that exclusively tuning Lewis or Bronsted acid sites does
the reaction temperature [324326], implying a synergic effect not promote acrolein production from glycerol, and that Bronsted
between Bronsted and Lewis acid sites on simultaneous esterica- acid sites with neighboring Lewis acid sites in a bifunctional cat-
tion and transesterication reactions in biodiesel production. alyst like zeolite ZSM-5 are necessary for two-step dehydration of
glycerol to acrolein. The two-step catalytic process might consist
2.4.5. Glycerol-derived chemicals of Bronsted acid sites initiating the reaction via dehydration of the
A signicant surge in biodiesel production will cause a surplus secondary hydroxyl groups of glycerol, and Lewis acid sites
of glycerol to exist, and thus glycerol is expected to be among the completing the reaction in a second reaction step through the de-
top 12 most important bio-based chemicals in the world [327]. Se- hydration of the primary hydroxyl groups to form acrolein (Fig. 17).
lected value-added chemicals that can be obtained from glycerol
through various pathways are shown in Fig. 15 [328]. Among these 2.4.6. Oxygen-containing precursors for diesel and jet fuels
pathways, the glycerol-to-acrolein dehydration is a typical acid- To form oxygen-containing precursors with carbon chain lengths
catalyzed reaction. in the range of the diesel (C9C 21 ) [334] and jet fuel (C8 C 16 )
Two different reaction pathways for glycerol dehydration have [335,336], CC coupling reaction of biomass-derived platform mol-
been proposed on the basis of the type of acid sites: (1) Bronsted ecules with carbon atoms no more than six is considered to be a
acid sites sequentially promote dehydration of the internal second- promising approach. The groups of Dumesic [337,338] and Huber
ary hydroxyl groups and primary hydroxyl groups of glycerol to afford [339] initially proposed the idea of making C8C15 alkanes with fur-
acrolein (Fig. 16a), while (2) Lewis acid sites exclusively catalyze one fural as the feedstock by successive aldol condensation, hydro-
step dehydration of the primary hydroxyl group of glycerol to genation and HDO. In this catalytic process, the aldol condensation
produce acetol (Fig. 16b) [329331]. Foo et al. [332] investigated the is eciently catalyzed by homogeneous and heterogeneous bases
H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194 119

Fig. 15. Value-added chemicals that can be produced from glycerol via catalytic pathways. Adapted with permission from Ref. 328, Copyright 2014 Elsevier.

[340343], however, solid acids are seldom employed. Kikhtyanin present in the small particles are prone to cleave CC bonds as com-
et al. [344,345] showed that both Lewis and Bronsted acid sites of pared with the low index planes that dominates in large particles.
zeolites (e.g., H-ZSM-5, H-Beta, H-MOR, H-USY and MWW) might In this respect, one more reason for the higher selectivity to C15
be involved in aldol condensation of furfural with acetone to yield alkanes over the Pt/ZrP catalyst can be the result of the larger Pt
4-(2-furyl)-3-buten-2-on (FAc) as well as a certain amount of 1,4- particle size in the Pt/ZrP catalyst that is helpful to prevent the unde-
pentandien-3-on-1,5-di-2-furanyl (F2Ac). Unlike base catalysts, an sirable CC cleavage reactions. Both the acidity of solid support and
additional product (FAc)2 was formed as a result of FAc dimeriza- the characteristics of the metal particles are two important factors
tion over Bronsted acid sites (Fig. 18). To determine the role of Lewis for improving catalytic activity for multiple-step reactions.
and Bronsted acidity in aldol condensation of furfural and acetone, Variation of reaction systems with BronstedLewis acid bifunc-
a number of metal organic framework (MOF) materials possess- tional catalytic materials allows a wide range of products to be
ing Lewis acidity have been investigated. Bronsted acidity, lead by formed. Further, by adjusting BronstedLewis acid sites, use of active
structural defects, rather than Lewis acidity of CuBTC (copper metals or supports along with relevant morphological structures,
benzene-1,3,5-tricarboxylate) or FeBTC (iron benzene-1,3,5- control of product distributions and reaction pathways is possi-
tricarboxylate) seems to be primarily responsible for the high ble. Bifunctional acidic materials are broadening the spectrum of
catalytic performance [346]. Likewise, hydroalkylation/alkylation biorenery products and accelerating practical methods for trans-
(HAA) of MF with biomass-derived aldehydes or ketones to carbon- forming biomass resources.
chain increased oxygenates could also be eciently catalyzed by
Bronsted acids [347352]. Pt-loaded ZrP bearing Bronsted and Lewis 3. Acidbase bifunctionalized materials
acidity showed enhanced catalytic performance for the subse-
quent hydrogenolysis reaction as compared with Pt-loaded Acids and bases can be used effectively in solid catalytic mate-
SiO2Al2O3, TiO2, and Nb2O5 catalysts [353]. In general, the specif- rials by spatially isolating acidic and basic sites [354]. Acidbase
ic activity of small metal particles is superior to large particle bifunctionality of a catalyst promotes chemical transformations via
counterparts, while the coordinatively unsaturated metal atoms active site isolation so that a wide range of biomass conversions are

Fig. 16. Proposed reaction pathways of glycerol dehydration on Bronsted acid sites (a) and Lewis acid sites (b). LAS-OH: Lewis acid site -OH. Adapted with permission from
Refs. 329 and 330, Copyright 2010; 2014 Elsevier.
120 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

m/c-ZrO2 has the highest amount of acid sites (0.67 mmol/g) and
base sites (0.55 mmol/g), whereas a-TiO2 has the highest density of
acid sites (0.08 mmol/m2) and base sites (0.04 mmol/m2) among
these compounds. The a-TiO2 has superior catalytic activity for the
glucose-to-HMF transformation (Table 4, Entries 46) [358]. In a
study of TiO2 and ZrO2 for glucose and fructose conversion in water
under microwave irradiation, Qi et al. [359] reported that solid base
ZrO2 could promote isomerization of glucose to 1,2-enediol (fruc-
tose), and HMF would be formed by an additional acidic condition
(Table 4, Entries 7 and 8). In this regards, ZrO2 in combination with
a solid acid SO42/TiO2SiO2 (3:4, w/w) catalyzes the degradation
of corn starch hydrolyzate (glucose solution) to attain HMF in a yield
of 48% (Table 4, Entry 9) [360].
To enhance the acidity of metal oxides, mineral acids such as H3PO4
and H2SO4 can be introduced by impregnation [387,388]. Acid-modied
oxides show enhanced reactivity in the dehydration of fructose and
glucose units to HMF (Table 4, Entries 1022). For example, sulfated zir-
conia (SO42/ZrO2) prepared by mixing zirconium hydroxide with 1M
H2SO4 and subsequent calcination gives a fructose conversion of 94%
with an HMF yield of 73% in acetoneDMSO mixtures (Table 4, Entry
10) [361]. Investigation on the bifunctionality of SO42/ZrO2 by further
incorporation of aluminum species in varied loadings was carried by
Yan et al. (Table 4, Entry 1113) [362]. Yang et al. found that with an
increase in Al content, the number of acid sites decrease while the
number of base sites increase so that an optimized HMF yield of
55% could be obtained from starch over SO42/ZrO2Al2O3 catalyst
Fig. 17. Proposed reaction pathway for the cooperativity of Bronsted and Lewis acid having a Zr/Al molar ratio of 1:1 (acidity: 1.55 mmol/g, basicity:
sites in glycerol dehydration. Adapted with permission from Ref. 333, Copyright 0.52 mmol/g) (Table 4, Entries 1416) [363]. Submonolayer SO4 cov-
2014 American Chemical Society.
erages in sulfated catalysts (SO4/ZrO2) with a suitable SO4 content
(~1.5 wt% SO4) offer an ideal balance of basic and LewisBronsted
possible when one considers acid-catalyzed and base-catalyzed acid sites (with a molar ratio of ~1/3.55) and promote isomeriza-
routes to a product [355]. Representative studies on catalytic trans- tion of glucose to fructose and subsequent dehydration of fructose
formation of biomass and its derivatives to selected chemicals are to HMF (Table 4, Entries 1722) [364].
discussed in the following sections. Hydrotalcite (HT), which shares some similar catalytic proper-
ties as ZrO2, is active for promoting isomerization of glucose to
3.1. HMF and furfural fructose, as well as xylose to xylulose [365,389], but HT is inactive
for hydrolysis/dehydration reactions (Table 4, Entries 2328) [366].
In hydrothermal systems, homogeneous alkali catalysts are ef- In the presence of both HT and Amberlyst-15, HMF is produced in
cient for promoting glucose isomerization to fructose and moderate yields (up to ~54%) from glucose, sucrose, and cellobi-
homogeneous acid catalysts are active for facilitating fructose de- ose in a polar aprotic solvent such as DMSO, N,N-dimethylformamide,
hydration to HMF (Table 4, Entries 13) [356,357]. Solid acidbase and DMA (Table 4, Entries 2936) [367,368]. Glucose/fructose and
catalysts, namely, metal oxides, anatase TiO2 (a-TiO2), rutile TiO2 (r- xylose/xylulose, galactose/tagatose and arabinose/ribulose are con-
TiO2) and monoclinic/tetragonal mixture ZrO2 (m/c-ZrO2) have been verted into HMF and furfural, respectively, and 5-methyl-2-
employed for the glucose-to-HMF transformation. The metal oxide, furaldehyde is produced from rhamnose/rhamnulose under the

Fig. 18. Reaction pathways for Aldol condensation between furfural and acetone. Adapted with permission from Ref. 344, Copyright 2014 Elsevier.
Table 4
Acidbase bifunctional materials and selected homogeneous catalytic systems used in the conversion of biomass-related substrates into value-added products with summary of reaction conditions, maximum catalytic activity
and catalyst reusability.

Entry Substrate Catalysta Acid/base Reaction conditions Main product Catalytic activity Reusability Ref.
ratio
Solvent Temp. Time Conv. Yield Cycles Yieldb

1 Glucose (10 wt%) 1 mmol/g H2SO4 1/0 H2O 220 C 5 min HMF 30% 2% NMc NM [356]
[Fructose] [3%]
2 Glucose (10 wt%) 1 mmol/g NaOH 0/1 H2O 220 C 5 min HMF 30% 2% NM NM [356]
[Fructose] [11%]
3 Glucose (10 wt%) 1 mmol/g H3PO4 1/0 H2O 200 C 5 min HMF 40% 4% NM NM [357]
4 Glucose (10 wt%) 100 wt% m/c-ZrO2 1.22/1 H2O 200 C 5 min HMF 50% 6% NM NM [358]
[Fructose] [13%]
5 Glucose (10 wt%) 100 wt% a-TiO2 2/1 H2O 200 C 5 min HMF 82% 20% NM NM [358]
[Fructose] [2%]
6 Glucose (10 wt%) 100 wt% r-TiO2 0.88/1 H2O 200 C 5 min HMF 22% 3% NM NM [358]
[Fructose] [5%]
7 Glucose (2 wt%) 50 wt% ZrO2 H2O 200 C 3 min HMF 48% 5% NM NM [359]

H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194


[Fructose] [26%]
8 Glucose (2 wt%) 50 wt% TiO2 H2O 200 C 3 min HMF 42% 8% NM NM [359]
[Fructose] [17%]
9 Glucose (50 wt%) 10 wt% ZrO2 + SO42/TiO2SiO2 3/4 H2O/DMSO (1:2, v/v) 120 C 12 h HMF 48% NM NM [360]
10 Fructose (2 wt%) 20 wt% SO42/ZrO2 Acetone/DMSO (7:3) 180 C 20 min HMF 94% 73% NM NM [361]
11 Glucose (7.6 wt%) 16.7 wt% SO42/ZrO2Al2O3 (Zr/Al : 1/1) 2.98/1 DMSO 130 C 4h HMF 72% 48% 5 35% [362]
12 Glucose (7.6 wt%) 16.7 wt% SO42/ZrO2Al2O3 (Zr/Al : 9/1) 5.11/1 DMSO 130 C 4h HMF 97% 27% NM NM [362]
13 Glucose (7.6 wt%) 16.7 wt% SO42/ZrO2Al2O3 (Zr/Al : 1/9) 0.97/1 DMSO 130 C 4h HMF 95% 37% NM NM [362]
14 Starch (4.5 wt%) 5.3 wt% SO42/ZrO2Al2O3 (Zr/Al : 1/1) 2.98/1 H2O/DMSO (1:5, v/v) 150 C 6h HMF 55% NM NM [363]
15 Starch (4.5 wt%) 16.7 wt% SO42/ZrO2Al2O3 (Zr/Al : 9/1) 5.11/1 H2O/DMSO (1:5, v/v) 150 C 6h HMF 38% NM NM [363]
16 Starch (4.5 wt%) 16.7 wt% SO42/ZrO2Al2O3 (Zr/Al : 1/9) 0.97/1 H2O/DMSO (1:5, v/v) 150 C 6h HMF 45% NM NM [363]
17 Glucose (0.5 wt%) 100 wt% ZrO2 1/1 H2O 100 C 6h HMF 21% <1% NM NM [364]
[Fructose] [18%]
18 Glucose (0.5 wt%) 100 wt% SO4/ZrO2 (1 wt% SO4) 3.25/1 H2O 100 C 6h HMF 23% 1% NM NM [364]
[Fructose] [19%]
19 Glucose (0.5 wt%) 100 wt% SO4/ZrO2 (1 wt% SO4) 3.25/1 H2O 120 C 6h HMF 42% 5% NM NM [364]
[Fructose] [30%]
20 Glucose (0.5 wt%) 100 wt% SO4/ZrO2 (1.5 wt% SO4) 3.55/1 H2O 100 C 6h HMF 21% 1% NM NM [364]
[Fructose] [16%]
21 Glucose (0.5 wt%) 100 wt% SO4/ZrO2 (5 wt% SO4) 10.33/1 H2O 100 C 6h HMF 12% 1% NM NM [364]
[Fructose] [8%]
22 Glucose (0.5 wt%) 100 wt% SO4/ZrO2 (5 wt% SO4) 10.33/1 H2O 120 C 6h HMF 37% 7% NM NM [364]
[Fructose] [15%]
23 Xylose (3.3 wt%) 100 wt% Amberlyst-15 1/0 N,N-dimethylformamide 100 C 3h Furfural 51% <1% NM NM [365]
24 Xylose (3.3 wt%) 100 wt% HT 0/1 N,N-dimethylformamide 100 C 3h Furfural 60% 0 NM NM [365]
25 Xylose (3.3 wt%) 100 wt% Amberlyst-15 + 100 wt% HT 1/1 N,N-dimethylformamide 100 C 3h Furfural 57% 24% NM NM [365]
26 Xylose (3.3 wt%) 100 wt% Amberlyst-15 + 200 wt% HT 1/2 N,N-dimethylformamide 100 C 3h Furfural 72% 37% NM NM [365]
27 Cellulose (0.3 wt%) 111.1 wt% HT 0.50/1 H2O 150 C 24 h Glucose 27% 11% NM NM [366]
28 Cellulose (0.3 wt%) 111.1 wt% HTOHCa 0.66/1 H2O 150 C 24 h Glucose 47% 40% NM NM [366]
(3.38 mg/L Ca)
29 Glucose (3.3 wt%) 100 wt% Amberlyst-15 + 200 wt% HT 1/2 N,N-dimethylformamide 80 C 9h HMF 73% 42% NM NM [367]
30 Sucrose (3.3 wt%) 100 wt% Amberlyst-15 + 100 wt% HT 1/1 N,N-dimethylformamide 120 C 3h HMF 58% 54% NM NM [367]
31 Cellobiose (3.3 wt%) 100 wt% Amberlyst-15 + 100 wt% HT 1/1 N,N-dimethylformamide 120 C 3h HMF 52% 35% NM NM [367]
32 Glucose (3.3 wt%) 100 wt% Amberlyst-15 1/0 N,N-dimethylformamide 100 C 3h AHG 69% 32% NM NM [368]
33 Glucose (3.3 wt%) 100 wt% HT 0/1 N,N-dimethylformamide 100 C 3h Fructose 62% 38% NM NM [368]
34 Glucose (3.3 wt%) 100 wt% Amberlyst-15 + 200 wt% HT 1/2 N,N-dimethylformamide 100 C 3h HMF 72% 41% 3 41% [368]
[Fructose] [4%]
(AHG) (10%)
35 Glucose (3.3 wt%) 100 wt% Amberlyst-15 + 200 wt% HT 1/2 DMA 100 C 3h HMF 97% 14% NM NM [368]
[Fructose] [ < 1%]
(AHG) (<1%)

121
(continued on next page)
122
Table 4 (continued)

Entry Substrate Catalysta Acid/base Reaction conditions Main product Catalytic activity Reusability Ref.
ratio
Solvent Temp. Time Conv. Yield Cycles Yieldb

36 Glucose (3.3 wt%) 100 wt% Amberlyst-15 + 200 wt% HT 1/2 DMSO 100 C 3h HMF 94% 12% NM NM [368]
[Fructose] [0]
(AHG) (<1%)
37 Xylose (3.3 wt%) 100 wt% Amberlyst-15 + 200 wt% Al2O3NiAl 1/2 N,N-dimethylformamide 100 C 8h Furfural 46% NM NM [369]
38 Arabinose/rhamnose/ 100 wt% Amberlyst-15 + 200 wt% HT 1/2 N,N-dimethylformamide 110 C 6h Furfural 97% 31% NM NM [370]
lactose (3.3 wt%) [MFD] [29%]
(HMF) (32%)
39 Glucose (50 wt%) 66.7 wt% Amberlyst-15 + 266.7 wt% 1/4 H2O/THF (1/10, v/v) 180 C 1.5 h HMF 87% 39% NM NM [371]
Na2ZrSi4O11
40 Glucose (10 wt%) 100 wt% ZrC 0/1 H2O 120 C 20 min Fructose 45% 34% 6 29% [372]
41 Glucose (10 wt%) 100 wt% Amberlyst-15 + 50 wt% ZrC 2/1 H2O/toluene (1/1, v/v) 120 C 12 h LA 41% 17% NM NM [372]
~50 wt% Amberlite IR120 (H+) + ~300 wt%

H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194


42 Sucrose (1.3 wt%) ~1/6 H2O or DMF 100 C 65 h HMF ~100% 50% NM NM [373]
Amberlite IRA-400 (OH) for
4 steps
43 Cellulose (1.3 wt%) ~26.7wt% LPMSN-both 0.81/1 [EMIM]Cl/H2O (9:1, v/v) 120 C 3h HMF 15% NM NM [374]
[Glucose] [36%]
44 Cellulose (1.3 wt%) ~26.7wt% LPMSNSO3H + LPMSNNH2 1/1 [EMIM]Cl/H2O (9:1, v/v) 120 C 3h HMF 19% NM NM [374]
[Glucose] [39%]
45 Glucose (6.7 wt%) 100 wt% P-VI-0 0/1 THF/DMSO (1.5/1, w/w) 100 C 10 h HMF 0 NM NM [375]
46 Glucose (6.7 wt%) 50 wt% PSO3H-154 1/0 THF/DMSO (1.5/1, w/w) 100 C 10 h HMF 0 NM NM [375]
47 Glucose (6.7 wt%) 50 wt% PSO3H-154 + 100 wt% P-VI-0 1/2 THF/DMSO (1.5/1, w/w) 100 C 10 h HMF 95% NM NM [375]
48 Fructose (4.5 wt%) 27.8 wt% Lys/PW(2) 6.1/1 EtOH/DMSO (7:3, v/v). 120 C 15 h EMF 100% 77% 6 ~70% [376]
[HMF] [9%]
49 HMF (2.5 wt%) 50 wt% ZrO(OH)2 EtOH 150 C 2.5 h BHMF 94% 84% 6 47% [377]
50 HMF (1.2 wt%) 1 mol % Sn-Beta (Sn/HMF molar ratio) 2-PrOH 180 C 6h BHMF bis-ether 92% 80% 2 55% [378]
51 HMF (8.0 wt%) 1 mol % Sn-Beta (Sn/HMF molar ratio) 2-PrOH 180 C 6h BHMF bis-ether 83% 48% [378]
52 HMF (1.0 wt%) 3 mol % Hf-Beta (Sn/HMF molar ratio) EtOH 120 C 24 h BHMF bis-ether 87% 67% [379]
53 HMF (1.0 wt%) 3 mol % Zr-Beta (Sn/HMF molar ratio) EtOH 120 C 24 h BHMF bis-ether 81% 54% [379]
54 Furfural (2.4 wt%) 208.3 wt% ZrPhyA 0.39/1 2-PrOH 100 C 2h FfA 99% 99% 5 98% [380]
55 FfA (2.9 wt%) 28.2 wt% SBA15-SO3H 1/0 1-BuOH 110 C 4h Butyl levulinate 100% 96% [381]
56 FfA (3.6 wt%) 1.5 wt% (12.5% SO3H) ArSO3HEt/PhHNS 1/0 EtOH 120 C 2h Ethyl levulinate 85% [382]
57 Vegetable oil (8.3 wt%) 5 wt% Li/ZrO2 MeOH 65 C 1.25 h FAME 99% 9 90% [383]
+ FFA (4.7 wt%)
58 Rapeseed oil (5 wt%) 3 wt% SO4/ZrO2 MeOH 200 C 1h FAME 86% 5 42% [384]
+ FFA (10 wt%)
59 Waste oil (70 wt%) 2.4 wt% ZnOLa2O3 MeOH 200 C 3h FAME 96% NM NM [385]
+ FFA (5.2 wt%)
60 Jatropha oil (4 wt%) 3 wt% CaOLa2O3 MeOH 160 C 3h FAME 99% 5 75% [386]
+ FFA (9 wt%)
61 Jatropha oil (4 wt%) 3 wt% CaO MeOH 120 C 3h FAME 96% 5 60% [386]
+ FFA (9 wt%)
62 Jatropha oil (4 wt%) 3 wt% La2O3 MeOH 160 C 3h FAME 23% NM NM [386]
+ FFA (9 wt%)
a Catalyst dosage relative to the substrate.
b
Product yield in the last cycle.
c
NM: not mentioned.
HMF: 5-hydroxymethylfurfural, EMF: 5-ethoxymethylfurfural, HT: hydrotalcite, AHG: anhydroglucose: sum of 1,6-anhydro--d-glucopyranose and 1,6-anhydro--d-glucofuranose, DMA: N,N-dimethylacetamide, DMSO: di-
methyl sulfoxide, MFD: 5-methyl-2-furaldehyde, THF: tetrahydrofuran, ZrC: zirconium carbonate, LA: levulinic acid, LPMSN: mesoporous silica nanoparticles with large pores, [EMIM]Cl: 1-ethyl-3-methylimidazolium chloride,
P-VI-0 is synthesized from copolymerization of divinylbenzene, 1-vinylimidazole and N,N-methylenediacrylamide with water contact angle of 0, P-SO3H-154: SO3H functionalized polymers with water contact angle of 154,
EMF: 5-ethoxymethylfurfural, BHMF: 2,5-bishydroxymethyl furan, PhyA: phytic acid, FfA: furfural alcohol, ArSO3HEtHNS: arenesulfonic acid functionalized ethane-bridged organosilica hollow nanospheres, FAME: fatty acid
methyl esters, FFA: free fatty acid.
H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194 123

Fig. 19. Schematic of the conversion of various sugars to the corresponding furans: 5-hydroxymethylfurfural (HMF), furfural, and 5-methyl-2-furaldehyde.

combined action of HT and Amberlyst-15 (Fig. 19; Table 4, Entry 37) Side-reactions of HMF hydration occurring on acidic sites with water
[369,370]. This catalytic system promotes mixtures of carbohy- molecules are likely to be inhibited by the basic sites [390,391]. Wang
drates containing arabinose, rhamnose, and lactose to produce et al. [375] designed and synthesized mesoporous acid catalysts
furfural (31% yield), 5-methyl-2-furaldehyde (MFD, 29% yield), and (PSO3H-x, x stands for the water contact angle on the surface of
HMF (32% yield), respectively, in N,N-dimethylformamide (Table 4, solid catalyst) with different water wettabilities including
Entry 38). Combined with the strongly acidic polymer resin superhydrophobic PSO3H-154, hydrophobic PSO3H-125 and
Amberlyst-15, a layered basic zirconosilicate Na2ZrSi4O11 is capable PSO3H-105, and hydrophilic PSO3H-44 [392]. Among these solid
of catalyzing glucose transformations to give HMF at 45% selectiv- acids, PSO3H-154 with superhydrophobic character is more favor-
ity and 87% glucose conversion (Table 4, Entry 39) [371]. A solid base able for isolating water molecules from the acidic sites and for
catalyst zirconium carbonate (ZrC) applied to the same reaction suppressing further hydration of HMF to LA. To realize one-pot trans-
affords 17% yield of LA after 12 h reaction in watertoluene biphasic formation of glucose to HMF, solid bases with controllable wettability
solvent (Table 4, Entries 40 and 41) [372]. The product distribu- (PVI-x) synthesized from copolymerization of divinylbenzene,
tion depends on the types of substrates, the reaction media, and 1-vinylimidazole and N,N-methylenediacrylamide have been pro-
the catalyst type. posed [375]. Although, the pure base catalyst (PVI-0) or pure acid
Other combined solid acidbase catalysts have been developed catalyst (PSO3H-154) is practically inactive for the formation of
for sugar-to-HMF conversions. Prez-Maqueda et al. [373] re- HMF, the combined catalysts, superhydrophobic PSO3H-154 and
ported an ecient catalytic process for the preparation of HMF from superhydrophilic PVI-0 give HMF with yields as high as 95% in
sucrose following a sequence of four steps (hydrolysis, dehydra- DMSOTHF (3:2, w/w) (Table 4, Entries 4547). The super-
tion, glucose/fructose isomerization and dehydration) catalyzed by hydrophobicity of the solid acid PSO3H-154 facilitates the isola-
reusable cation- and anion-exchange resins, Amberlite IR120 (H+) tion of the acidic sites from water molecules and inhibits the
and Amberlite IRA-400 (OH) to give an isolated HMF yield of 50% hydration of HMF while the superhydrophilic base PVI-0 pro-
(Table 4, Entry 42). Peng et al. [374] synthesized a series of motes glucose-to-fructose isomerization, thus, their combination
mesoporous silica nanoparticles (MSNs) with large pore sizes (ca. gives superior catalytic performance.
30 nm) functionalized with acid (SO3H, denoted as LPMSNSO3H),
base (NH2, LPMSNNH2) and both acidbase (SO3H and NH2, 3.2. HMF- and furfural-derivatives
LPMSN-both) functional groups with a grafting method. A mixture
of LPMSNSO3H and LPMSNNH2 (1:1, w/w), and LPMSN-both ex- As discussed in Section 2.4, catalytic sequential dehydration and
hibits comparable ecacy for one-pot cellulose-to-HMF conversion etherication of carbohydrates into EMF proceeds in the presence
in an IL [EMIM]Cl in the presence of a trace amount of water (Table 4, of both homogeneous and heterogeneous catalysts with Bronsted
Entries 43 and 44), and good yields of glucose and HMF are ob- acidic sites and Lewis acidic sites (Fig. 13). Nevertheless, relatively
tained for LPMSNSO3H and LPMSNNH2 mixed catalyst (~39 and low yields of EMF are always observed, owing to the lack of cata-
19%, respectively) and LPMSN-both (36 and 15%, respectively). lytic sites for etherication of HMF with ethanol as well as the low
124 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

Fig. 20. Catalytic routes for conversion of 5-hydroxymethylfurfural (HMF) and furfural into value-added products with acidbase bifunctional materials. FfA: furfuryl alcohol,
BHMF: 2,5-bis(hydroxymethyl)furan.

stability of EMF that tends to be converted into EL [393]. Consid- 1.32 mmol/g) and Lewis acidic sites (Zr4+, 0.51 mmol/g). In the cata-
ering that the catalytic activity of etherication can be controlled lytic process, 2-propanol is adsorbed onto ZrPhyA, followed by
by both the surface basicity and Lewis acidity [394396], a series dissociation to the corresponding alkoxide and H species by the acid
of nanocatalysts functionalized with both acidic and basic sites was basic sites (Zr4+O2), thus increasing the reaction rate of the MPV
synthesized from the self-assembly of the corresponding basic amino reaction. As a downstream product of furfural, alkyl levulinates can
acids with PTA [376]. These obtained acidbase bifunctional hybrid be synthesized through cascade hydrogenation (with Lewis acid
nanospheres that act as heterogeneous catalysts are effective for the base sites) and alcoholysis (with Bronsted acid sites) in alcohols
conversion of fructose, sucrose and inulin to EMF and give an EMF (Table 4, Entries 55 and 56) [381,382]. It can be concluded that the
yield of 77% through sequential dehydrationetherication reac- distribution of products derived from HMF and furfural can be ad-
tion over Lys/PW(2) in EtOH/DMSO (Table 4, Entry 48). The justed by controlling the content and type of acidbase sites in a
nanocatalyst Lys/PW(2) functionalized with acid (1.28 mmol/g) and bifunctional solid catalyst.
base (0.21 mmol/g) sites is able to be reused six times with EMF
yields slightly decreasing from 77% to ~70%. In this cascade cata- 3.3. Biodiesel
lytic process, solid acid sites promote the dehydration of fructose
to HMF in ethanol, and the subsequent etherication is promoted Apart from enzymatic and Bronsted/Lewis acid-mediated cata-
by both surface basicity through deprotonation of alcohol and Lewis lytic processes [398402], biodiesel can be eciently produced
acidity by facilitating the elimination of the OH group. through simultaneous esterication and transesterication reac-
Catalytic transfer hydrogenation between OH of alcohols and tions promoted by acidbase bifunctional catalysts. As compared
C:O of furan aldehydes can be facilitated by acidbase pair sites with acid-catalyzed transesterication of vegetable oils, base-
through MeerweinPonndorfVerley (MPV) reduction [397]. Hao catalyzed reactions proceed faster and are less corrosive, therefore,
et al. [377] demonstrated that ethanol could be used as hydrogen industrial processes usually favor base catalysts [403,404]. The tra-
donor and solvent for catalytic transfer hydrogenation of biomass- ditional homogeneous base-mediated catalytic process is simple and
derived HMF to 2,5-bishydroxymethyl furan (BHMF) over low- fast, but the neutralization/washing step requires the consump-
cost ZrO(OH) 2 , with a maximum BHMF yield of 89% at HMF tion of acids, and generates acid/base wastes [405]. Moreover, soap
conversion of 94% being obtained (Table 4, Entry 49). The OH formation occurs under homogeneous alkaline catalysis when the
groups and ZrO species of ZrO(OH)2 successively contribute to weak raw oils contain more than 1 wt% of total FFAs [406,407]. A two-
basic and Lewis acidic sites, which are important for the activity step process of acid-catalyzed esterication followed by base-
of the MPV reaction. However, the presence of excess acid sites cata- catalyzed transesterication is commonly employed to resolve the
lyzes BHMF to its ether counterparts (Fig. 20). The increase of problems of saponication, slow reaction rate and biodiesel sta-
substrate concentration accelerates the self-etherication of HMF, bility in biodiesel production with high FFA content for which the
thus directly leads to a decrease in selectivity toward BHMF and its process involves multiple reactions, washing, and separation
bis-ether product (Table 4, Entries 5053) [378,379]. Therefore, ap- stages [408,409]. Impregnation of extra active sites (i.e., Al2O3 and
propriate substrate concentration and number of acidbase sites are KOH) into ZrO2 possessing both acidity and basicity [410] is an ef-
important for obtaining desired yields of etheried products. cient approach for catalyzing simultaneous esterication and
When furfural is used as substrate, Song et al. [380] demon- transesterication of raw oils containing high FFAs (Table 4, Entries
strated that zirconium phosphonate (ZrPhyA) synthesized from 57 and 58) [383,384]. Through investigating the catalytic perfor-
phytic acid (PhyA) reacting with ZrCl4 is active for the selective MPV mance of three thermally robust ZrO2-based catalysts including
reduction in 2-propanol, affording furfuryl alcohol (FfA) with a yield titania zirconia (TiZ), sulfated zirconia (SZ), and tungstated zirco-
of 99% (Table 4, Entry 54). The good performance of ZrPhyA is due nia (WZ) for esterication and transesterication, Lpez et al. [411]
to the formation of in situ basic sites (O2 in phosphate groups, found that TiZ bearing relatively higher basicity has the lowest
H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194 125

activity for esterication but is more active than WZ for


transesterication. Sulfated zirconia is the most active catalyst (on
a weight basis) for both transesterication and esterication reac-
tions examined by Lpez et al. [411], although it exhibits signicant
sulfur loss that greatly reduces its long-term activity.
Lanthanum can affect zinc oxide distribution, as well as in-
crease the surface acid and base sites, because of the strong
interaction between Zn and La species [385]. Among possible Zn/
La catalysts, Zn 3 La 1 was found to simultaneously catalyze oil
transesterication and FFA esterication reactions in a single-
step, while minimizing oil and biodiesel hydrolysis. High yields (up
to 96%) of fatty acid methyl esters (FAMEs) are obtained even using
unrened or waste oils (Table 4, Entry 59). Integration of Ca and La
metal oxides enhance their catalytic activity in simultaneous Fig. 21. Schematic of ethanol-to-isobutene transformation: (a) reaction pathway,
transesterication and esterication reactions as compared with sole (b) overall reaction. Adapted with permission from Ref. 414, Copyright 2011 Amer-
bulk CaO and La2O3 (Table 4, Entries 6062) [386,412], which may ican Chemical Society.
be attributed to the increased surface acidic and basic sites that
become activated by dispersed CaO on the composite surface. During
esterication, the interaction of the carbonyl oxygen of FFAs with obtained from 1,3-propanediol dehydration over these acidbase
the Lewis acidic site of the catalyst is speculated to assist in the for- catalysts, owing to the absence of a secondary OH group. For the
mation of carbocation and the subsequent nucleophilic attack of the case of glycerol-to-acrolein dehydration, the reactivity is con-
alcohol that produces FAMEs via elimination of water molecule from trolled by the strength, type and the amount of the acidic sites and
a tetrahedral intermediate. In a parallel reaction of transesterication, hindering as much as possible the number, strength and action of
methanol is adsorbed onto the Lewis base site of the catalyst to form the basic sites [418]. The combined use of acidbase catalysis favors
oxygen anion, followed by nucleophilic attack to the esters pro- glycerol transesterication and carbonylation with urea to give glyc-
ducing two kinds of esters through the break of hydroxyl groups erol carbonate [419], etherication to short-chain polyglycerols [420],
of a tetrahedral intermediate. Therefore, appropriate control of acid and steam reforming to hydrogen [421]. Some reactions such as
base site distribution can facilitate one-pot production of biodiesel cascade isomerizationdehydrationKnoevenagel condensation
from triglycerides with high content of FFAs through concurrent [422], tandem deacetalization-nitroaldol [423], and cooperative aldol
transesterication and esterication reactions. condensation [424] can be implemented with acidbase bifunc-
tional catalysts. Co-existence of acidbase sites in a single catalyst
3.4. Other methods and biomass-derived chemicals at some level provides a degree of cooperative catalysis that have
enhanced catalytic performance compared with physical mix-
Acid/base catalysis plays an important role in most practical tures of monofunctional catalysts. Acidbase bifunctional catalytic
biofuel processes such as esterication and transesterication of plant materials greatly expand the scope of development for biomass
oils containing FFAs with alcohols to produce biodiesel, and transformations.
pretreatment/hydrolysis of lignocellulose to fermentable sugars for
bioethanol production [413]. However, shortcomings of catalysts with 4. Acid/basemetal bifunctionalized materials
single acid or single base sites are encountered. In the case of bio-
diesel production over a basic catalyst, the presence of FFAs and Biomass reneries deal with highly-oxygenated compounds that
water always leads to the formation of soaps and the diculty in are upgraded to moderately-oxygenated and deoxygenated plat-
the catalyst and product separation. form molecules. Dehydration, etherication, CC coupling reactions
including aldol-condensation, ketonization, oligomerization and
3.4.1. Nanosized mixed oxides for obtaining isobutene from hydroxyalkylation over acid and base catalysts are capable of re-
bio-ethanol moving oxygen functionalities and increasing carbon number of the
A range of related reaction pathways for upgrading biomass- feedstock compounds [425]. Some of the challenges for convert-
derived molecules with high eciency have been realized by acid ing biomass into products are related to the ecient cleavage of
base catalysis. Nanosized ZnxZryOz mixed oxides with balanced acid alcoholic CO linkages within the feedstock molecules to reduce
and base sites can directly catalyze the conversion of bio-ethanol both degree of polymerization and oxygen content, as well as the
to isobutene in yields as high as ~83% at 450 C with a steam to selective oxidation of OH into specic functional groups. Pre-
carbon ratio (S/C) of 5 and residence time of 0.11 sgmL1 (Fig. 21) cious metal catalysts (e.g., Au, Pd, Pt and Ru) and non-precious metal
[414]. The addition of ZnO into ZrO2 selectively passivates strong catalysts (e.g., Fe, Cu and Ni) with the presence of acid/base addi-
Lewis acidic sites and weakens Bronsted acidic sites of zirconia, but tives or supports exhibit good activities for hydrogenation/
enhances the basicity [414]. Basic catalysts such as ZnOCaO and hydrogenolysis and oxidation reactions [426428]. Synthetic
ZnOFe2O3 are effective for the conversion of ethanol to acetone procedures for these supported metal nanoparticles, impregna-
[415], although the selective transformation of acetone into isobutene tion, calcination and subsequent reduction of metal ions with H2,
requires microporous acidic zeolites [416]. A specic microporous NaBH4, carbon/CO, and alcohols are frequently adopted. This section
environment in zeolites does not appear to be a critical factor in introduces advances in metal nanoparticles combined with acid/
the ZnZr materials for selectively producing isobutene from acetone, base catalysis for transformation of biomass derivatives into chemical
possibly due to the moderate Bronsted acidity of ZnxZryOz cata- products.
lysts [416]. Acetone can be formed from gas-phase dehydration of
1,2-propanediol in the presence of basic catalyst such as CeO2 and 4.1. Production of oxygenates
MgO, while strongly acidic catalysts (8.2 < H0 3.0) show high se-
lectivity for propanol as compared with basic (H +7.2) and acidic 4.1.1. Oxidation of sugars and polyols
catalysts with either weaker (3.0 < H0 +6.8) or stronger acidity The selective oxidation of alcohols in aqueous solution over sup-
(H 0 8.2) [417]. In contrast, a wide range of products are ported metal catalysts is facilitated by high-pH conditions. Oxygen
126 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

atoms originating from hydroxide ions formed via catalytic decom- degradation of cellulose to formic acid with 35% yield (Table 5, Entry
position of a peroxide intermediate instead of molecular oxygen are 16), where it was speculated that cellulose was rst hydrolyzed into
incorporated into the alcohol during the oxidation reaction [429] glucose, followed by oxidation involving electron and oxygen trans-
so that the acidity of the support can play a role in the activity and fer processes to produce formic acid (Fig. 22) [449]. In this process,
selectivity of the catalysts [430]. In this regard, acid or base prop- catalytic oxidation to formic acid and deep hydrolysis to byproducts
erties are essential for metal-catalyzed oxidation processes with high proceeds in a competitive way that can be adjusted by changing O2
conversion rates and selectivities. Cooperative effects between metal partial pressure, reaction temperature and acid concentration
particles and solid support related to structure and textural char- (Table 5, Entries 1721) [450453]. Together with formic acid, some
acteristics inuence the selective oxidation of alcohols [431]. other organic acids such as lactic acid, acetic acid, and glycolic acid
Anaerobic and aerobic conversions of carbohydrates promoted by are also formed from sugars via sequential reactions (Table 5, Entries
bi- or multifunctional catalysts are two important renewable routes 2229) [454456].
to produce organic acids and aldehydes/ketones [432]. In these cata- Starting from polyols, formic acid can be generated via oxida-
lytic processes, conversions and selectivities to target products tion processes. For instance, Zhang et al. [457] reported that
depend on oxidants, pH values, catalysts, and reactor operating con- V-substituted phosphomolybdic acids were active for oxidation of
ditions [433436]. When the pH of the reaction solution is glycerol to formic acid in highly concentrated aqueous solutions with
unregulated, strong adsorption of acids onto a metal surface occurs, molecular oxygen, and 3.64 g formic acid was produced from 10 g
causing the poisoning of metal catalysts during oxidation of sugars glycerol/water (50/50, w/w) solution (Table 5, Entries 30 and 31).
[437]. To prevent inactivation of metal particles, buffering of reac- In an aqueous solution of Lewis acid (e.g., FeCl3, ZnCl2, CrCl3 or AlCl3),
tion solutions is necessary when using this approach for selective Ru(OH)4/r-GO catalyst prepared via reuxing, RuCl3 aqueous solu-
conversion of biomass derivatives that involve oxidation. tion containing graphite oxide (GO) promotes the oxidation of
Selective oxidation of sugars could produce commercially rele- glycerol to formic acid (Table 5, Entries 3235) [458]. A synergis-
vant polyoxy-acids, such as gluconic acid, which is widely used in tic effect between Ru(OH)4/r-GO and FeCl3 is observed for glycerol
the chemical, food, pharmaceutical and textile industries. Glu- oxidation such that high formic acid yields (ca. 60%) are obtained.
conic acid is produced via selective oxidation of glucose in the C1 The oxidation of C3 oxygenates to C1 oxygenates might simultane-
position [438]. Much attention has been paid to the production of ously yield the C2 (C3C2+C1) products. For the case of glycerol
gluconic acid via liquid phase oxidation catalyzed by metal par- oxidation, Kapkowski et al. [459] detected that solgel SiO 2 -
ticles such as Pd and Au (Table 5, Entries 13) [439441]. In supported Au affords high acetic acid yields (up to 90%) besides single
comparison to monometallic systems, bimetallic catalysts are capable carbonaceous products with glycerol conversion of 100% in a dilute
of enhancing reactivity, but typically exhibit low stability because and viscous H2O2/H2O liquid phase (Table 5, Entry 36). Bimetallic
of metal leaching that occurs during reaction (Table 5, Entries 4-8) Au/Cu and Au/Ni catalysts obtained by nano-Au transfer show com-
[442,443]. Metal oxide supported catalysts are more active for parable performance, while Cu or Ni leaching results in deactivation
glucose-to-gluconic acid transformation than supported or free metal of these catalysts during the reaction. A large number of oxidized
colloids (Table 5, Entry 9) [444], and they have relatively higher sta- chemicals including dihydroxyacetone, glyceric acid, lactic acid,
bility over the long-term than other solid supports such as carbon hydroxypyruvic acid, dihydroxymalonic acid, glycolaldehyde,
[464,465]. Table 5 shows that base sites resulting from solvents, solid glycoxylic acid, glycolic acid, oxalic acid, tartronic acid, mesoxalic
supports, or co-existent metal oxides are helpful to increase the se- acid and other unstable intermediates can be produced via
lectivity toward gluconic acid from glucose oxidation. When chemoselective oxidation of glycerol (Fig. 23) by controlling the type
biopolymers (e.g., cellobiose and cellulose) are used as substrate, of the support, the size of the metal particles, and the acid/base prop-
acidity is necessary for hydrolysis to occur before intermediate prod- erties of the reaction medium [466468]. Control of product
ucts can be oxidized. selectivity is necessary for ecient valorization of glycerol in con-
Acidbase pairs combined with metal particles (Table 5) seem sideration of its wide product distribution for different catalytic
to be exclusively used for the oxidation of saccharides. Under base- processes. Nanoparticles promoted by acid/base solid supports or
free conditions, Rautiainen et al. [445] demonstrated that microwave reaction media, in most cases, show good selectivity for the desired
heating could provide an ecient catalytic system for the oxida- products in the chemoselective oxidation of glycerol, but lead to rel-
tion of glucose to gluconic acid (76 % yield) in the presence of atively low glycerol conversions owing to three hydroxyl groups that
supported Au nanoparticles (Table 5, Entry 10). In contrast, have similar reactivity. Therefore, the development of robust nano-
Wojcieszak et al. [446] reported that glucuronic acid, except glu- sized bifunctional catalysts is necessary for practical glycerol
conic acid, is the dominant oxidized product from glucose over Au/ oxidation. Moreover, the use of bifunctional catalysts for biodiesel
CeO2 and AuCs/CeO2 under oil heating and base-free conditions production as well as for subsequent glycerol conversion will improve
(Table 5, Entries 11 and 12). The improved activity of the Au cata- process eciency and economics.
lyst after being doped with Cs may be the result of an increase in Lactic acid is produced mainly by anaerobic conversion of sugars
local surface basicity caused by CsOH species. However, many re- with fermentation [469]. Lactic acid can also be produced by Lewis
action mechanisms involving acidbase properties of the catalysts acidmediated catalytic processes involving successive hydrolysis
are not well understood yet, so that detailed studies on this topic of polysaccharides to glucose, glucose-to-fructose isomerization,
are needed. retro-aldol fragmentation to trioses (i.e., dihydroxyacetone and glyc-
Formic acid is a promising medium for both hydrogen storage eraldehydes), and dehydration and 1,2-hydride shift reactions
and production, and it is also an important commodity chemical. [470,471]. In an aerobic process, the catalytic dehydrogenation of
By using a Keggin-type polyoxometalate (H5PV2Mo10O40) as homo- sorbitol, mannitol, xylitol and erythritol to lactic acid can be achieved
geneous catalyst, p-toluenesulfonic acid as additive, oxygen as oxidant with a series of IrNHC complexes under basic conditions, afford-
and water as solvent, water-insoluble biomass such as wood, waste ing a maximum lactic acid yield of ~50% (Table 5, Entries 3740)
paper, cyanobacteria and xylan can be transformed into formic acid [460]. Catalytic dehydrogenation of mannitol and xylitol, mannose
with up to 53% yield (Table 5, Entry 13) [447]. Without the addi- and xylose gives similar oxidized product mixtures as those of sor-
tion of strong acid, water-soluble glucose is oxidized into formic acid bitol aerobic transformation; base-driven isomerization and
in yields of up to 49% with molecular oxygen (Table 5, Entry 14) [448] dehydration of simple sugars account for the catalyst selectivity. In
and up to 52% with air (Table 5, Entry 15) [449] over H5PV2Mo10O40. light of these observations, it has been speculated that the conver-
The H5PV2Mo10O40 has been used as a bifunctional catalyst for the sion of sorbitol to lactic acid occurs as shown in Fig. 24 [460]. Initially,
Table 5
Acid/base catalytic systems used in the conversion of carbohydrates into organic acids with summary of reaction conditions, oxidant, maximum catalytic activity and catalyst reusability.

Entry Substrate Catalysta Reaction conditions Oxidant Main product Catalytic activity Reusability Ref.
b
Solvent Temp. Time Conv. Yield Cycles Yield

1 Glucose (10 wt%) 5.0 wt% PdBi/C Basic H2O 40 C 155 min 0.1 MPa Air Gluconic acid 100% 99% 5 99% [439]
2 Cellobiose (0.5 wt%) 1.0 wt% Au/Amberlyst-15 H2O 100 C 24 h 0.1 MPa Air Gluconic acid 45% 4 40% [440]
3 Glucose (1.8 wt%) 0.94 wt% Au/CMK-3 H2O 110 C 2h 0.3 MPa O2 Gluconic acid 92% 80% NMc NM [441]
4 Glucose (4.5 wt%) 5 wt% PdTe/SiO2 H2O 60 C 2h 0.1 MPa Air Gluconic acid 100% 100% 10 86% [442]
5 Glucose (4.5 wt%) 5 wt% Pd/SiO2 H2O 60 C 2h 0.1 MPa Air Gluconic acid 59% 44% 10 22% [442]
6 Cellobiose (1.0 wt%) 0.5 wt% AuCu/TiO2 H2O 145 C 3h 1 MPa O2 Gluconic acid 100% 89% 4 ~70% [443]

H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194


7 Cellobiose (1.0 wt%) 0.5 wt% Cu/TiO2 H2O 145 C 3h 1 MPa O2 Gluconic acid 98% 62% NM NM [443]
8 Cellobiose (1.0 wt%) 0.5 wt% Au/TiO2 H2O 145 C 3h 1 MPa O2 Gluconic acid 98% 74% NM NM [443]
9 Glucose (20.0 wt%) 0.3% Au/Al2O3 Basic H2O 40 C 5190 mmol min1gAu1 0.9 MPa O2 Gluconic acid 100% 99% NM NM [444]
10 Glucose (2.2 wt%) 1.8 wt% Au/Al2O3 H2O 120 C 10 mind 2.2 equiv. H2O2 Gluconic acid 87% 76% 4 >60% [445]
11 Glucose (9.9 wt%) 1.7 wt% Au/CeO2 H2O 70 C 4h 1.5 MPa O2 Glucuronic acid 12% 11% NM NM [446]
12 Glucose (9.9 wt%) 2.5 wt% AuCs/CeO2 H2O 70 C 4h 1.5 MPa O2 Glucuronic acid 55% 54% NM NM [446]
13 Xylan (2.7 wt%) TSA + 4.2 mol% H5PV2Mo10O40 H2O 90 C 24 h 3.0 MPa O2 Formic acid 97% 53% NM NM [447]
14 Glucose (3.0 wt%) 4.4 mol% H5PV2Mo10O40 H2O 80 C 7h 3.0 MPa O2 Formic acid 100% 49% NM NM [448]
15 Glucose (2.5 wt%) 5 mol% H5PV2Mo10O40 H2O 100 C 3h 5.0 MPa Air Formic acid 100% 52% NM NM [449]
16 Cellulose (1.0 wt%) 5 mol% H5PV2Mo10O40 H2O 170 C 9h 5.0 MPa Air Formic acid 100% 35% NM NM [449]
17 Cellulose (1.7 wt%) 0.35 wt% NaVO3 + 2 wt% H2SO4 H2O 160 C 10 min 3.0 MPa O2 Formic acid 58% NM NM [450]
18 Wheat straw (0.8 wt%) 0.35 wt% NaVO3 + 2 wt% H2SO4 H2O 160 C 5 min 3.0 MPa O2 Formic acid 100% 47% 4 46% [451]
[Acetic acid] [7%] [7%]
19 Xylan (1.7 wt%) 0.35 wt% NaVO3 + 0.7 wt% H2SO4 H2O 160 C 30 min 3.0 MPa O2 Formic acid 100% 64% 5 63% [452]
20 Cellulose (6.7 wt%) 38.8 wt% H4PMo11O40 H2O 180 C 1h 1.0 MPa O2 Formic acid 100% 36% NM NM [453]
[CO2] [63%]
21 Cellulose (6.7 wt%) 38.8 wt% IL-PMo H2O 180 C 1h 1.0 MPa O2 Formic acid 100% 51% 3 50% [453]
[CO2] [41%] [42%]
22 Cellulose (0.9 wt%) 10 mol% VOSO4 H2O 160 C 2h 2.0 MPa O2 Formic acid 39% NM NM [448]
23 Cellulose (0.9 wt%) 5 mol% VOSO4 H2O 180 C 2h 2.0 MPa N2 Formic acid 4% NM NM [454]
[Lactic acid] [54%]
24 Cellulose (1.0 wt%) 10 mol% H4PVMo11O40 H2O 180 C 3h 0.6 MPa O2 Formic acid 100% 68% 4 65% [455]
[Acetic acid] [12%] [15%]
25 Cellulose (5.0 wt%) 10 mol% H4PVMo11O40 H2O 180 C 3h 2.0 MPa O2 Formic acid 35% NM NM [455]
[Acetic acid] [16%]
26 Glucose (1 wt%) 24.3 mol% H3PMo12O40 H2O 180 C 1h 0.6 MPa O2 Glycolic acid 96% 42% NM NM [456]
[Formaic acid] [15%]
(Acetic acid) (6%)
27 Cellulose (1 wt%) 24.3 mol% H3PMo12O40 H2O 180 C 1h 0.6 MPa O2 Glycolic acid 49% 9 50% [456]
[Formaic acid] [10%]
(Acetic acid) (4%)
28 Bagasse (1 wt%) 24.3 mol% H3PMo12O40 H2O 180 C 1h 0.6 MPa O2 Glycolic acid 32% NM NM [456]
[Formic acid] [10%]
(Acetic acid) (11%)
(continued on next page)

127
128
Table 5 (continued)

Entry Substrate Catalysta Reaction conditions Oxidant Main product Catalytic activity Reusability Ref.

Solvent Temp. Time Conv. Yield Cycles Yieldb

29 Hay (1 wt%) 24.3 mol% H3PMo12O40 H2O 180 C 1h 0.6 MPa O2 Glycolic acid 28% NM NM [456]
[Formic acid] [8%]
(Acetic acid) (7%)
30 Glycerol (50 wt%) 0.2 mol% H6PV3Mo9O40 H2O 150 C 3h 4.0 MPa O2 Formic acid 95% 51% NM NM [457]
[Acetic acid] [11%]

H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194


31 Glycerol (1.0 wt%) 10 mol% H6PV3Mo9O40 H2O 150 C 3h 2.0 MPa O2 Formic acid 100% 60% NM NM [457]
[Acetic acid] [3%]
32 Glycerol (1.9 wt%) FeCl3 + 0.1 mol% Ru(OH)4/r-GO H2O 160 C 1h 0.5 MPa O2 Formic acid 96% ~60% NM NM [458]
[Acetic acid] [1%]
33 Glycerol (1.9 wt%) AlCl3 + 0.1 mol% Ru(OH)4/r-GO H2O 160 C 1h 0.5 MPa O2 Formic acid 92% 39% NM NM [458]
[Acetic acid] [3%]
34 Glycerol (1.9 wt%) CrCl3 + 0.1 mol% Ru(OH)4/r-GO H2O 160 C 1h 0.5 MPa O2 Formic acid 80% 18% NM NM [458]
[Acetic acid] [7%]
35 Glycerol (1.9 wt%) ZnCl2 + 0.1 mol% Ru(OH)4/r-GO H2O 160 C 1h 0.5 MPa O2 Formic acid 30% 10% NM NM [458]
[Acetic acid] [5%]
36 Glycerol (1.9 wt%) 0.1 wt% Au/SiO2 H2O 80 C 24 h 37 equiv. H2O2 Acetic acid 100% 90% 4 60% [459]
37 Sorbitol (3.5 wt%) 0.1 mol% [(5-C5Me5)Ir(IMe)2Cl]BF4 160 C 24 h Atmospheric N2 Lactic acid 49% 40% NM NM [460]
38 Mannitol (3.5 wt%) 0.1 mol% [(5-C5Me5)Ir(IMe)2Cl]BF4 160 C 24 h Atmospheric N2 Lactic acid 54% 43% NM NM [460]
39 Xylitol (3.5 wt%) 0.1 mol% [(5-C5Me5)Ir(IMe)2Cl]BF4 160 C 24 h Atmospheric N2 Lactic acid 56% 49% NM NM [460]
40 Erythritol (3.5 wt%) 0.1 mol% [(5-C5Me5)Ir(IMe)2Cl]BF4 160 C 24 h Atmospheric N2 Lactic acid 16% 12% NM NM [460]
41 Glycerol (1.0 wt%) 5 wt% Ru/C H2O + NaOH 200 C 5h 4.0 MPa O2 Lactic acid 100% 34% NM NM [461]
[Propylene glycol] [19%]
42 Glycerol (1.0 wt%) 3 wt% Pt/C H2O + NaOH 200 C 5h 4.0 MPa O2 Lactic acid 92% 44% NM NM [461]
[Propylene glycol] [42%]
43 Glycerol (1.0 wt%) 3 wt% Pt/C H2O + CaO 200 C 5h 4.0 MPa O2 Lactic acid 100% 58% NM NM [461]
[Propylene glycol] [36%]
44 Glycerol (1.0 wt%) 3 wt% PtRu/C H2O 200 C 5h 4.0 MPa O2 Lactic acid 42% 0 NM NM [462]
[Propylene glycol] 10%
(Ethylene glycol) [21%]
45 Glycerol (1.0 wt%) 3 wt% PtRu/C H2O + NaOH 200 C 5h 4.0 MPa O2 Lactic acid 100% 37% NM NM [462]
[propylene glycol] [18%]
(ethylene glycol) (2%)
46 Glucose (0.45 wt%) 400 mol% [IMEP]Cl H2O + NaOH 100 C 30 min 0.1 MPa N2 Lactic acid 99% 63% 6 54% [463]
a Metal loading of the catalyst or catalyst dosage relative to the substrate.
b Product yield in the last cycle.
c NM: not mentioned.
d
Microwave irradiation.
CMK-3: an ordered mesoporous carbon, TSA: p-toluenesulfonic acid, IL-PMo: ionic liquids composed of HPMo11O403 and SO3H functionalized methylimidazole cations, [IMEP]Cl: polymerization of imidazole and epichlorohydrin.
H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194 129

Fig. 22. Possible reaction pathway for catalytic oxidation of glucose with H5PV2Mo10O40 though electron and oxygen transfer processes. Adapted with permission from Ref.
449, Copyright 2012 Wiley-VCH.

iridium-catalyzed dehydrogenation of sorbitol to a tautomeric depending on the type of C6 sugar. Dihydroxyacetone and glycer-
mixture containing glucose, fructose and galtose occurs under basic aldehyde from fructose could act as direct precursors to lactate via
conditions (KOHH2O) [472], followed by a retro-aldol condensa- an intramolecular Cannizzaro reaction (Table 5, Entries 4145)
tion, cleaving CC bonds, to form two different C3 molecules [461,462]. In the case of glucose, two potential enol molecules formed

Fig. 23. Catalytic oxidation of glycerol to various ne chemicals. Adapted with permission from Ref. 466, Copyright 2011 Royal Society of Chemistry.
130 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

Fig. 24. Proposed reaction pathway from sorbitol to lactic acid through glucose and fructose. Adapted with permission from Ref. 460, Copyright 2014 Royal Society of
Chemistry.

via dehydration lead to totally different products, in which the furan-containing polymers and materials that has special proper-
2-hydroxy enol is converted to a 1,2-di-ketone, followed by cleav- ties [474479]. Several oxidants such as H2O2, 2,2,6,6-tetramethyl-
age to yield two C3 molecules that both are then converted to lactic piperidin-1-oxyl (TEMPO), and classical metal oxides containing
acid, while the 3-hydroxy enol results in the formation of C2 and chromium or manganese can be used although toxicity and waste
C4 products (Table 5, Entry 46) [463,473]. Thus, suppressing the for- treatment issues exist [480482]. Thus, the use of dioxygen as
mation of 3-hydroxy enol by adjusting acidity/basicity of reaction oxidant with the only byproduct being water is a current research
solution or solid support is helpful to increase the selectivity of lactic topic with the goal to convert HMF into FDCA via oxidation (Table 6).
acid. Under alkaline conditions, carbon-supported ruthenium is re-
In the catalytic conversion of carbohydrates to organic acids, the ported to be an active catalyst for HMF-to-FDCA conversion, but it
synergistic effect of metal and acidbase sites seems to be a major is associated with low stability (Table 6, Entries 13) [483,484]. Ru-
factor that affects product selectivity. In some cases, sugars can be thenium on different magnesium-based supports including
eciently converted to the desired molecules, however, appropri- magnesium oxide, spinel, and HT show superior catalytic perfor-
ate control of the functionalities of the catalytic materials still needs mance for the selective oxidation of HMF to FDCA [485], as compared
research for application in practical bioreneries. with other solid supports such as titanium-, aluminum-, cerium-,
zirconium-, and lanthanum oxides, magnetite, and hydroxyapa-
4.1.2. Oxidation of HMF and furfural tite (Table 6, Entries 411). Catalysts with high basicity generally
4.1.2.1. 2,5-Furandicarboxylic acid (FDCA). Furanic compounds bearing exhibit high eciency for the HMF-to-FDCA oxidation in aqueous
oxygenated groups such as CHO and COOR (R: H, CH3, CnH2n+1) media without adding free base, and FDCA yields higher than 90%
derived from biomass derivatives are expected to replace fuels and have been obtained (Table 6, Entries 4 and 6). In these reaction
chemicals presently being produced from fossil fuels. FDCA, systems (Table 6, Entries 411), a homogeneous alkaline mixture
generated from selective oxidation of HMF, is a monomer for is formed in the case of both HT and MgO supports by partial
Table 6
Catalytic oxidation of 5-hydroxymethylfurfural, carbohydrates and furfural derivatives with summary of reaction conditions, oxidant, maximum catalytic activity and catalyst reusability.

Entry Substrate Catalysta Reaction conditions Oxidant Main Product Catalytic Reusability Ref.
activity

Solvent Temp. Time Conv. Yield Cycles Yieldb


c
1 HMF (4.8 wt%) 5 wt% Pt/Al2O3 Basic H2O 60 C 160 min 0.02 MPa O2 FDCA 100% 95% NM NM [483]
2 HMF (1.3 wt%) 5 wt% Pd/Al2O3 Basic H2O 60 C 160 min 0.02 MPa O2 FDCA 100% 50% NM NM [484]
3 HMF (1.3 wt%) 5 wt% Ru/Al2O3 Basic H2O 60 C 160 min 0.02 MPa O2 FDCA 100% 75% NM NM [484]
4 HMF (0.6 wt%) 5 mol% Ru(OH)x/MgO H2O 140 C 6h 0.25 MPa O2 FDCA 100% 92% NM NM [485]
5 HMF (0.6 wt%) 5 mol% Ru(OH)x/Spinel H2O 140 C 6h 0.25 MPa O2 FDCA 100% 40% NM NM [485]
6 HMF (0.6 wt%) 5 mol% Ru(OH)x/HT H2O 140 C 6h 0.25 MPa O2 FDCA 100% 90% NM NM [485]
7 HMF (0.6 wt%) 5 mol% Ru(OH)x/TiO2 H2O 140 C 6h 0.25 MPa O2 FDCA 100% 21% NM NM [485]
8 HMF (0.6 wt%) 5 mol% Ru(OH)x/Al2O3 H2O 140 C 6h 0.25 MPa O2 FDCA 100% 23% NM NM [485]
9 HMF (0.6 wt%) 5 mol% Ru(OH)x/Fe3O4 H2O 140 C 6h 0.25 MPa O2 FDCA 100% 48% NM NM [485]

H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194


10 HMF (0.6 wt%) 5 mol% Ru(OH)x/ZrO2 H2O 140 C 6h 0.25 MPa O2 FDCA 100% 37% NM NM [485]
11 HMF (0.6 wt%) 5 mol% Ru(OH)x/CeO2 H2O 140 C 6h 0.25 MPa O2 FDCA 100% 38% NM NM [485]
12 HMF (2.9 wt%) 2.5 wt% Ru(OH)x/La2O3 [EMIm][OAc] 100 C 5h 3.0 MPa O2 FDCA 99% 48% NM NM [486]
13 HMF (1.3 wt%) 1 wt% Au/TiO2 Basic H2O 30 C 18 h 2.0 MPa O2 FDCA 100% 71% NM NM [487]
14 HMF (1.9 wt%) 2 mol% Au/CeO2 Basic H2O 65 C 8h 1.0 MPa O2 FDCA 100% 100% NM NM [488]
15 HMF (1.9 wt%) 2 mol% Au/TiO2 Basic H2O 65 C 8h 1.0 MPa O2 FDCA 100% 99% NM NM [488]
16 HMF (1.9 wt%) 2 mol% Au/Fe2O3 Basic H2O 65 C 8h 1.0 MPa O2 FDCA 100% 15% NM NM [488]
[HMFCA] [85%]
17 HMF (1.9 wt%) 2 mol% Au/C Basic H2O 65 C 8h 1.0 MPa O2 FDCA 100% 44% NM NM [488]
[HMFCA] [56%]
18 HMF (2.1 wt%) 2 mol% Au/HT H2O 90 C 20 h 0.34 MPa O2 FDCA 100% 99% NM NM [489]
19 HMF(2.1 wt%) 2 mol% Au/TiO2 H2O 95 C 7h 1.0 MPa O2 FDCA 100% 99% 3 90% [490]
20 HMF (1.3 wt%) 2.0 wt% AuCu/TiO2 Basic H2O 95 C 6h 1.0 MPa O2 FDCA 100% 99% 5 >90% [491]
21 HMF (1.3 wt%) 1.5 wt% AuCu/TiO2 Basic H2O 60 C 6h 1.0 MPa O2 FDCA 31% NM NM [491]
22 HMF (1.3 wt%) 1.5 wt% Au/TiO2 Basic H2O 60 C 6h 1.0 MPa O2 FDCA 13% 3 2% [491]
23 HMF (1.3 wt%) 0.36 wt% Cu/TiO2 Basic H2O 60 C 6h 1.0 MPa O2 FDCA 0 NM NM [491]
24 HMF (0.45 wt%) 1.0 wt% AuPd/CNT Basic H2O 100 C 12 h 0.5 MPa O2 FDCA 100% 94% NM NM [492]
[DFF] [0]
25 HMF (0.45 wt%) 1.0 wt% Au/CNT Basic H2O 100 C 12 h 0.5 MPa O2 FDCA 78% 11% NM NM [492]
[DFF] [30%]
26 HMF (0.45 wt%) 1.0 wt% Pd/CNT Basic H2O 100 C 12 h 0.5 MPa O2 FDCA 63% 7% NM NM [492]
[DFF] [25%]
27 HMF (1.3 wt%) 1.5 wt% AuCu/CeO2 Basic H2O 70 C 6h 1.0 MPa O2 FDCA 100% 90% NM NM [493]
[HMFCA] [10%]
28 HMF (1.3 wt%) 1.5 wt% Au/CeO2 Basic H2O 70 C 6h 1.0 MPa O2 FDCA 100% 55% NM NM [493]
[HMFCA] [45%]
29 HMF (1.9 wt%) 3.0 wt% Pt/C Basic H2O 22 C 6h 0.69 MPa O2 FDCA 100% 79% NM NM [494]
[HMFCA] [21%]
30 HMF (1.9 wt%) 3.0 wt% Pd/C Basic H2O 22 C 6h 0.69 MPa O2 FDCA 100% 71% NM NM [494]
[HMFCA] [29%]
31 HMF (1.9 wt%) 0.8 wt% Au/C Basic H2O 22 C 6h 0.69 MPa O2 FDCA 100% 7% NM NM [494]
[HMFCA] [93%]
32 HMF (1.9 wt%) 1.6 wt% Au/TiO2 Basic H2O 22 C 6h 0.69 MPa O2 FDCA 100% 8% NM NM [494]
[HMFCA] [92%]

33 HMF (3.0 wt%) Co(OAc)2/Zn(OAc)2/Br H2O 90 C 4.5 h Atmospheric O2 DFF 100% 96% NM NM [495]
34 HMF (3.0 wt%) Co(OAc)2/Zn(OAc)2/ H2O 90 C 3h Atmospheric O2 FDCA 90% 60% NM NM [495]
Br + HTFA [FFCA] [29%]
35 HMF (3.0 wt%) 1.9 wt% Au/TiO2 H2O 130 C 3h Atmospheric O2 FFCA 62% 45% NM NM [495]
(continued on next page)

131
132
Table 6 (continued)

Entry Substrate Catalysta Reaction conditions Oxidant Main Product Catalytic Reusability Ref.
activity

Solvent Temp. Time Conv. Yield Cycles Yieldb

36 HMF (3.0 wt%) 1.9 wt% Au/TiO2 + HTFA H2O 130 C 3h Atmospheric O2 FFCA 84% 79% NM NM [495]
37 HMF (3.0 wt%) 1.9 wt% Au/CeO2 H2O 130 C 3h Atmospheric O2 FFCA 29% 19% NM NM [495]
38 HMF (3.0 wt%) 1.9 wt% Au/CeO2 + HTFA H2O 130 C 3h Atmospheric O2 FFCA 83% 71% NM NM [495]
39 HMF (3.0 wt%) 5 wt% Pt/ZrO2 Acidic H2O 100 C 75 min 1.0 MPa air FFCA 80% 56% NM NM [496]
40 HMF (3.0 wt%) 5 wt% Pt/ZrO2 Acidic H2O 140 C 15 min 1.0 MPa O2 FDCA 100% 85% NM NM [496]
41 HMF (3.0 wt%) 5 wt% Pt/SiO2 Basic H2O 100 C 15 min 1.0 MPa air FDCA 100% 100% NM NM [496]
42 HMF (3.0 wt%) 5 wt% Pt/SiO2 H2O 100 C 60 min 1.0 MPa air DFF 90% 41% NM NM [496]
[FFCA] [38%]
43 Fructose (1.0 wt%) 5 wt% PtBi/C + Lewatit SPC H2O/MIBK 70 C 70 h 1.0 MPa air FDCA 25% NM NM [497]
108

H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194


44 Fructose (1.7 wt%) 5 wt% Co(acac)3/SiO2 H2O/MIBK 160 C 65 min 2.0 MPa air FDCA 72% 71% NM NM [498]
45 HMF (2.0 wt%) 2.1 wt% Fe3+POP-1 H2O 100 C 10 h 1.0 MPa air FDCA 100% 79% NM NM [499]
46 HMF (1.4 wt%) Merrield resin- CH3CN 100 C 24 h t-BuOOH FDCA 96% 90% 6 60% [500]
CoPy (70 C)
47 HMF (0.3 wt%) 1 mol% Pd/PVP Basic H2O 90 C 7h 0.1 MPa O2 FDCA 99% 93% NM NM [501]
48 HMF (0.5 wt%) 3.5 wt% Pt/Al2O3 Basic H2O 75 C 12 h 0.1 MPa O2 FDCA 96% 96% NM NM [502]
49 HMF (2.0 wt%) 7 mol% Li2CoMn3O8 Basic H2O 150 C 8h 5.5 MPa O2 FDCA 100% 80% NM NM [503]
50 HMF (1.3 wt%) 1 mol% Pt/ZrO2 Basic H2O 100 C 24 h 4.0 MPa O2 FDCA 97% 95% NM NM [504]
51 HMF (1.3 wt%) 1 mol% Pt/TiO2 Basic H2O 100 C 12 h 4.0 MPa O2 FDCA 100% 96% 4 95% [504]
52 HMF (0.6 wt%) 5.4 wt% Pd/C@Fe3O4 Basic H2O 80 C 6h 0.1 MPa O2 FDCA 98% 87% 5 84% [505]
53 HMF (0.6 wt%) 2.5 wt% -Fe2O3@HAPPd Basic H2O 100 C 6h 0.1 MPa O2 FDCA 97% 93% 5 92% [506]
54 Fructose (2.5 wt%) Fe3O4@SiO2SO3H/ DMSO 100 C 12 h 75 wt% t-BuOOH FDCA 99% 60% 6 ~60% [507]
nano-Fe3O4CoOx
55 HMF (4.7 wt%) 0.05 wt% Co/Mn/Br/Zr H2O 75 C 2h 7.0 MPa air DFF 100% 61% NM NM [508]
56 HMF (4.7 wt%) 0.05 wt% Co/Mn/Br H2O 75 C 2h 7.0 MPa air DFF 92% 65% NM NM [508]
57 HMF (2.9 wt%) 10 mol% CuCl22H2O DMSO 130 C 72 h Atmospheric air DFF 46% 46% NM NM [509]
58 HMF (2.9 wt%) 10 mol% Cu/PVP Toluene 130 C 72 h Atmospheric air DFF 66% 48% NM NM [509]
59 HMF (2.9 wt%) 3.3 mol% VO/PVP Toluene 130 C 24 h 0.1 MPa air DFF 75% 62% NM NM [509]
60 HMF (2.9 wt%) 3.3 mol% VO/PVP TFT 130 C 4h 1 MPa air DFF 77% 76% 2 64% [509]
61 HMF (2.9 wt%) 3.3 mol% VO/PVP Basic TFT 130 C 24 h 1 MPa air DFF 82% 81% NM NM [509]
62 HMF (2.9 wt%) 3.3 mol% VO/SBA Basic TFT 130 C 24 h 1 MPa air DFF 50% 49% NM NM [509]
63 HMF (3.0 wt%) 1.3 wt% FeVOP Dimethylformamide 100 C 8h 0.1 MPa O2 DFF 59% 51% NM NM [510]
64 HMF (3.0 wt%) 2.6 wt% CrVOP Dimethylformamide 100 C 8h 0.1 MPa O2 DFF 63% 43% NM NM [510]
65 HMF (3.0 wt%) 2.6 wt% GaVOP Dimethylformamide 100 C 8h 0.1 MPa O2 DFF 55% 32% NM NM [510]
66 HMF (3.0 wt%) 2.6 wt% MgVOP Dimethylformamide 100 C 8h 0.1 MPa O2 DFF 74% 58% NM NM [510]
67 HMF (3.0 wt%) 2.6 wt% CuVOP Dimethylformamide 100 C 8h 0.1 MPa O2 DFF 21% 18% NM NM [510]
68 HMF (3.0 wt%) 2.6 wt% PdVOP Dimethylformamide 100 C 8h 0.1 MPa O2 DFF 49% 29% NM NM [510]
69 HMF (0.3 wt%) 5.1 wt% VOx/TiO2 Toluene 90 C 1.6 MPa air DFF ~30% 21% NM NM [511]
70 HMF (0.3 wt%) 8.0 wt% VOx/ZrO2 Toluene 90 C - 1.6 MPa air DFF ~30% 21% NM NM [511]
71 HMF (0.3 wt%) 9.0 wt% VOx/Al2O3 Toluene 90 C 1.6 MPa air DFF ~30% 17% NM NM [511]
72 HMF (0.3 wt%) 3.0 wt% VOx/Nb2O5 Toluene 90 C 1.6 MPa air DFF ~30% 22% NM NM [511]
73 HMF (0.3 wt%) 5.5 wt% VOx/MgO Toluene 90 C 1.6 MPa air DFF ~30% 13% NM NM [511]
74 HMF (1.3 wt%) 1.3 mol% Ru/C Toluene 110 C 2.0 MPa O2 DFF ~30% 29% NM NM [512]
75 HMF (1.3 wt%) 1.3 mol% Ru/Mg2AlOx Toluene 110 C 2.0 MPa O2 DFF ~30% 28% NM NM [512]
76 HMF (1.3 wt%) 1.3 mol% Ru/MgO Toluene 110 C 2.0 MPa O2 DFF ~30% 6% NM NM [512]
77 HMF (1.3 wt%) 1.3 mol% Ru/Al2O3 Toluene 110 C 2.0 MPa O2 DFF ~30% 25% NM NM [512]
78 HMF (1.3 wt%) 1.3 mol% Ru/ZSM-5 Toluene 110 C 2.0 MPa O2 DFF ~30% 4% NM NM [512]
79 HMF (1.3 wt%) 1.3 mol% Ru/TiO2 Toluene 110 C 2.0 MPa O2 DFF ~30% 17% NM NM [512]
(continued on next page)
Table 6 (continued)

Entry Substrate Catalysta Reaction conditions Oxidant Main Product Catalytic Reusability Ref.
activity

Solvent Temp. Time Conv. Yield Cycles Yieldb

80 HMF (1.3 wt%) 1.3 mol% Ru/ZrO2 Toluene 110 C 2.0 MPa O2 DFF ~30% 20% NM NM [512]
81 HMF (1.3 wt%) 1.3 mol% Ru/CeO2 Toluene 110 C 2.0 MPa O2 DFF ~30% 18% NM NM [512]
82 HMF (1.3 wt%) 1.3 mol% Ru/C Benzotriuoride 110 C 2.0 MPa O2 DFF ~30% 28% NM NM [512]
83 HMF (1.3 wt%) 1.3 mol% Ru/C 1,4-Dioxane 110 C 2.0 MPa O2 DFF ~30% 12% NM NM [512]
84 HMF (1.3 wt%) 1.3 mol% Ru/C H2O 110 C 2.0 MPa O2 DFF ~30% 25% NM NM [512]
85 HMF (1.3 wt%) 1.3 mol% Ru/C DMSO 110 C 2.0 MPa O2 DFF ~30% 25% NM NM [512]
86 HMF (1.3 wt%) 1.3 mol% Ru/C Dimethylformamide 110 C 2.0 MPa O2 DFF ~30% 14% NM NM [512]
87 Glucose (8.0 wt%) 6 mol% CrCl36H2O/NaBr DMA 100 C 6h 21 mol% HMF 5 54% [513]
[110 C] [20 h] NaVO32H2O [DFF] [55%]
88 Fructose (6.0 wt%) Fe3O4SBASO3H DMSO 100 C 2h+6h Air + O2 ow HMF 99% 81% NM NM [514]

H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194


+ KOMS-2 (1:1) [DFF] [80%]
89 Glucose (6.0 wt%) Fe3O4SBASO3H DMSO 100 C 2h+6h Air + O2 ow HMF 99% NM NM [514]
+ KOMS-2 (1:1) [DFF] [ < 5%]
90 Inulin (6.0 wt%) Fe3O4SBASO3H DMSO 100 C 2h+6h Air + O2 ow HMF 99% NM NM [514]
+ KOMS-2 (1:1) [DFF] [29%]
91 Glucose (3.3 wt%) HT + Amberlyst-15 + Ru/HT Dimethylformamide 120 C 3h+6h N2 ow + O2 ow HMF 98% 9% NM NM [515]
(1:1:1) [DFF] [25%]
92 HMF (1.0 wt%) 15 wt% Ag/OMS-2 2-Propanol 165 C 6h 1.5 MPa Air DFF 100% 99% NM NM [516]
93 HMF (1.3 wt%) 3 wt% Ru/C Toluene 110 C 2.0 MPa O2 DFF 30% 29% 5 25% [517]
94 HMF (1.3 wt%) 3 wt% Ru/C Toluene 110 C 7h 2.0 MPa O2 DFF 100% 29% NM NM [517]
[FFCA] [52%]
(FDCA) (8%)
95 HMF (1.3 wt%) 3 wt% Ru/C + HT Toluene 110 C 6h 2.0 MPa O2 DFF 100% 1% NM NM [517]
[FFCA] [83%]
(FDCA) (5%)
96 HMF (1.3 wt%) 3 wt% Ru/C + HT Toluene 110 C 8h 2.0 MPa O2 DFF 100% 0 NM NM [517]
[FFCA] [3%]
(FDCA) (75%)
97 HMF (25.2 wt%) 2 mol% VOSO4 + 2 mol% CH3CN 80 C 1.5 h 0.1 MPa O2 DFF 99% 98% NM NM [518]
Cu(NO3)2
98 HMF (1.0 wt%) 0.93%V0.26%Cu/ CH3CN 140 C 4h 4.0 MPa Air DFF 100% 98% 3 98% [519]
sulfonated carbon
99 HMF (1.8 wt%) 10 mol% RuCo(OH)2CeO2 MIBK 120 C 12 h O2 ow DFF 96% 83% 5 75% [520]
[FDCA] [9%]
100 Fructose (10 wt%) 50 wt% Cs3HPMo11VO40 DMSO 110 C 2h+6h 0.1 MPa N2 HMF 99% 72% 4 53% [521]
+ 0.1 MPa O2 [DFF] [60%]
120 C
101 Fructose (4.5 wt%) 11.1 wt% Cs0.5H2.5PMo12 DMSO 160 C 4h Atmospheric air DFF 69% 5 52% [522]
102 HMF (1.3 wt%) 39.7 wt% KMn8O16nH2O Dimethylformamide 110 C 1h 0.5 MPa O2 DMF 100% 97% NM NM [523]
103 Fructose (10 wt%) 50 wt% g-C3N4(H+) DMSO 130 C 2h+6h 0.1 MPa N2 HMF 99% 80% NM NM [524]
0.1 MPa O2 [DFF] 63%
104 HMF (1.0 wt%) 5 mol% V2O5/AC MIBK 100 C 4h 0.2 MPa O2 DFF 95% 92% 2 62% [525]
105 HMF (1.3 wt%) 80 wt% Polyaniline- 4-Chlorotoluene 100 C 12 h 0.1 MPa O2 DFF 99% 86% 6 75% [526]
VO(acac)2
106 HMF (2.0 wt%) 10 wt% V2O5/Beta Dimethylformamide 125 C 180 min 1.0 MPa O2 DFF 84% 83% NM NM [527]
107 HMF (1.3 wt%) 2 mol% Cu(NO3)2/NHPI CH3CN 50 C 7h 0.1 MPa O2 DFF 71% NM NM [528]
108 HMF (8.4 wt%) 20 mol% CuI + 7.5 mol% DMSO 130 C 10 h 0.3 MPa O2 DFF 93% 92% NM NM [529]
HBT
(continued on next page)

133
134
Table 6 (continued)

Entry Substrate Catalysta Reaction conditions Oxidant Main Product Catalytic Reusability Ref.
activity

Solvent Temp. Time Conv. Yield Cycles Yieldb

109 HMF (1.3 wt%) 2.2 wt% RuPVP/CNT Dimethylformamide 120 C 12 h 2.0 MPa O2 DFF 100% 94% NM NM [530]
110 HMF (0.8 wt%) 2.5 mol% Ru/CTF MTBE 80 C 1h 2.0 MPa O2 DFF 86% 55% NM NM [531]
111 HMF (5.6 wt%) 5 wt% PdV(3:2)@MIL-101 DMSO 140 C 10 h 0.1 MPa O2 DFF 100% 40% NM NM [532]
[HMF] [34%]
112 HMF (6.3 wt%) 30 mol% HBr or 30 mol% DMSO 150 C 18 h Atmospheric air DFF 100% 85% NM NM [533]
NaBr
113 HMF (1.8 wt%) 133.3 wt% Mn3O4/Fe3O4 Dimethylformamide 120 C 4h O2 ow DFF 100% 82% NM NM [534]
114 HMF (6.3 wt%) 2 mol% Toluene + AcOH 50 C 12 h 0.1 MPa O2 DFF 100% 99% 5 97% [535]
MNST + TEMPOSiO2@
Fe3O4

H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194


115 HMF (1.4 wt%) 2 wt% Ru-HAP@Fe2O3 4-Chlorotoluene 90 C 4h O2 ow DFF 100% 89% 6 80% [536]
116 HMF (1.4 wt%) 1.4 wt% Ru(III)NH2 Toluene 120 C 16 h Atmospheric air or DFF 100% 87% 6 81% [537]
SiO2@Fe3O4 O2 ow
117 HMF (6.3 wt%) 5 mol% VO(acac)2 CH3CN 90 C 4h 0.1 MPa O2 MA 15% <1% NM NM [538]
[DFF] [7%]
118 HMF (6.3 wt%) 5 mol% VO(acac)2 CH3CN 90 C 4h 1.0 MPa O2 MA 100% 52% NM NM [538]
[DFF] [14%]
119 HMF (9.2 wt%) 0.8 mol% CH3CN +AcOH 90 C 8h 1.0 MPa O2 MA 32% NM NM [539]
H5PV2Mo10O40xH2O [FA] [32%]
120 Furfural (15 vol%) H4PMo12O40/Cu(NO3)2 (2:1) H2O 98 C 14 h 2.0 MPa O2 MA 95% 50% NM NM [540]
121 Furfural (11.5 wt%) H5PV2Mo10O40/Cu(CF3SO3)2 CH3CN 110 C 14 h 2.0 MPa O2 MA 99% 54% NM NM [541]
(1:1)
122 Furfural (1.6 kPa) 8.9 wt% VOx/Al2O3 H2O 320 C 5.7 kPa O2 MA 100% 73% NM NM [542]
123 Furfural (4.6 wt%) 4.6 wt% Titanium silicalite H2O 50 C 24 h 12.3 wt% H2O2 MA 100% 78% NM NM [543]
124 Furfural (4.6 wt%) 4.6 wt% Titanium silicalite H2O 50 C 28 h (52 h) 7.2 wt% H2O2 MA 100% 80% 6 45% [543]
+ Amberlyst 70 (92%) (7 h)
125 Xylose (3.0 wt%) Vanadyl pyrophosphate H2O 300 C 10 vol% O2 MA 100% 25% NM NM [544]
[Acrylic acid] [17%]
(Acrolein) (11%)
126 Xylose (3.0 wt%) Iron molybdate H2O 300 C 10 vol% O2 MA 100% 2% NM NM [544]
[Acrylic acid] [3%]
(Acrolein) (2%)
127 Xylose (3.0 wt%) Molybdenum H2O 300 C 10 vol% O2 MA 100% 2% NM NM [544]
trioxide-cobalt oxide [Acrylic acid] [3%]
(Acrolein) (7%)
128 HMF (4.0 wt%) 0.3 mol% Au/TiO2 MeOH + CH3ONa 130 C 3h 0.4 MPa O2 FDMC 100% 98% NM NM [545]
129 HMF (1.3 wt%) 2.1 wt% Au/CeO2 MeOH 130 C 5h 1.0 MPa O2 FDMC 99% 98% 5 96% [545]
130 Furfural (1.3 wt%) 2.1 wt% Au/CeO2 MeOH 130 C 5h 1.0 MPa O2 MFA 99% 90% NM NM [545]
131 Furfural (0.2 wt%) 1.2 wt% Au/ZrO2 MeOH 60 C 90 min 0.6 MPa O2 MFA 25% 25% NM NM [546]
132 Furfural (0.2 wt%) 1.2 wt% Au/ZrO2 MeOH 120 C 90 min 0.1 MPa O2 or Air MFA 100% 90% NM NM [546]
133 HMF (0.2 wt%) 1.2 wt% Au/ZrO2 MeOH 130 C 5h 0.1 MPa O2 MFA 100% 30% NM NM [546]
134 Furfural (0.2 wt%) 1.0 wt% Au/ZrO2 MeOH 120 C 90 min 0.6 MPa O2 MFA 82% 74% 2 70% [547]
135 Furfural (0.2 wt%) 2.2 wt% Au/CeO2 MeOH 120 C 90 min 0.6 MPa O2 MFA 66% 46% 2 42% [547]
136 Furfural (0.2 wt%) 1.2 wt% Au/TiO2 MeOH 120 C 90 min 0.6 MPa O2 MFA 20% 18% 2 7% [547]
137 HMF (0.2 wt%) 1.5 wt% Au/TiO2 MeOH 130 C 5h 0.3 MPa O2 FDMC 90% 5% NM NM [548]
138 HMF (0.2 wt%) 1.5 wt% Au/ZrO2 MeOH 130 C 5h 0.3 MPa O2 FDMC 100% 23% NM NM [548]
139 HMF (0.2 wt%) 1.5 wt% Au/ZrO2-SO4 MeOH 130 C 5h 0.3 MPa O2 FDMC 100% 32% NM NM [548]
(continued on next page)
Table 6 (continued)

Entry Substrate Catalysta Reaction conditions Oxidant Main Product Catalytic Reusability Ref.
activity

Solvent Temp. Time Conv. Yield Cycles Yieldb

140 Levulinic acid 5.0 wt% Ru-MNP H2O 150 C 6h 1.0 MPa O2 Succinic acid 54% 52% 4 53% [549]
(0.6 wt%)
141 Furfural (3.2 wt%) 52.1 wt% Amberlyst-15 H2O 80 C 24 h 30 wt% H2O2 Succinic acid 100% 74% 3 70% [550]

H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194


142 Methyl levulinate 10 mol% p-TsOH MeOH 80 C 6h 200 mol% H2O2 Methyl succinate 56% 34% NM NM [551]
(0.8 wt%) [Methyl acetate] [22%]
143 Methyl levulinate 10 mol% MeSO3H MeOH 80 C 6h 200 mol% H2O2 Methyl succinate 48% 26% NM NM [551]
(0.8 wt%) [Methyl acetate] [22%]
144 Methyl levulinate 10 mol% H2SO4 MeOH 80 C 6h 200 mol% H2O2 Methyl succinate 54% 33% NM NM [551]
(0.8 wt%) [Methyl acetate] [21%]
145 Methyl levulinate 10 mol% TfOH MeOH 80 C 6h 200 mol% H2O2 Methyl succinate 49% 30% NM NM [551]
(0.8 wt%) [Methyl acetate] [19%]
146 Methyl levulinate 10 mol% Amberlyst-15 MeOH 80 C 6h 200 mol% H2O2 Methyl succinate 13% 8% NM NM [551]
(0.8 wt%) [Methyl acetate] [5%]
147 Methyl levulinate 10 mol% Hf(OTf)4 MeOH 80 C 6h 200 mol% H2O2 Methyl succinate 36% 21% NM NM [551]
(0.8 wt%) [Methyl acetate] [14%]
148 Methyl levulinate 10 mol% Hg(OTf)2 MeOH 80 C 6h 200 mol% H2O2 Methyl succinate 40% 19% NM NM [551]
(0.8 wt%) [Methyl acetate] [19%]
149 Methyl levulinate 10 mol% Sc(OTf)3 MeOH 80 C 6h 200 mol% H2O2 Methyl succinate 38% 19% NM NM [551]
(0.8 wt%) [Methyl acetate] [13%]
150 Levulinic acid 435 mol% KOH + [10 wt% H2O + [MeOH] 0 C 6h+ 30 wt% H2O2 2 3-(Hydroperoxy)propanoic 100% 80% NM NM [552]
(1.7 wt%) Pd/C] [40 min] + [0.38 MPa H2] acid + 3-hydroxypropanoic
acid
151 Levulinic acid 79 wt% HTFA H2O 90 C 20 min 30 wt% H2O2 Succinic acid 100% 60% NM NM [553]
(20.0 wt%)
a Metal loading of the catalyst or catalyst dosage relative to the substrate.
b
Product yield in the last cycle.
c NM: not mentioned.

HMF: 5-hydroxymethylfurfural, FDCA: 2,5-furandicarboxylic acid, HT: hydrotalcite, [EMIm][OAc]: 1-ethyl-3-methylimidazolium acetate, HMFCA: 5-hydroxymethyl-2-furancarboxylic acid, DFF: 2,5-diformylfuran, CNT: carbon
nanotube, FFCA: 5-formyl-2-furancarboxylic acid, HTFA: triuoroacetic acid, Lewatit SPC 108: a microporous cationic ion exchanger in H+ form, MIBK: methyl isobutyl ketone, Co(acac)3: cobalt acetylacetonate, Fe3+-POP-1: Fe3+-
porous organic polymer, Merrield resin-Co-Py: Merrield resin supported Co(II)meso-tetra(4-pyridyl)-porphyrin, t-BuOOH: tert-butyl hydroperoxide, PVP: polyvinyl pyrrolidone, TFT: triuorotoluene, K-OMS-2: H0.2K0.8Mn8O16nH2O
is an octahedral molecular sieve, NHPI: N-hydroxyphthalimide, HBT: 1-hydroxybenzotriazole, PVP/CNT: poly(4-vinylpyridine)-functionalized carbon-nanotube, CTF: covalent triazine frameworks, MTBE: methyl t-butyl ether,
AcOH: acetic acid, MNST: immobilized nitroxyl radical, TEMPO: 2,2,6,6-tetramethylpiperidine-N-oxide, HAP: hydroxyapatite, MA: maleic anhydride, FDMC: 2,5-dimethylfuroate, MFA: methyl furoate, MNP: magnetic nanoparticles,
p-TsOH: p-toluenesulfonic acid, MeSO3H: methane sulfonic acid, TfOH: triic acid.

135
136 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

Fig. 25. Proposed reaction pathway for aqueous HMF (5-hydroxymethylfurfural) aerobic oxidation. HMFCA: 5-hydroxymethyl-2-furancarboxylic acid, FFCA: 5-formyl-2-
furancarboxylic acid, FDCA: 2,5-furandicarboxylic acid. Adapted with permission from Ref. 488, Copyright 2009 Wiley-VCH.

dissolution of Mg2+ ions under the reaction conditions, resulting in oxidation to afford FDCA in an almost constant yield of >99%, 92%
the generation of Mg-FDCA salts that are stabilized against further and 90% for the rst, second and third runs, respectively (Table 6,
degradation. Among these salts, the spinel form remains stable and Entry 19). To further enhance the reusability and stability of gold
allows the oxidation reaction to proceed under base-free condi- nanoparticles, Pasini et al. [491] show that a relatively stronger syn-
tions [554]. By using ILs as the reaction solvent, Sthlberg et al. [486] ergistic effect in terms of sample stability and resistance to poisoning
found that Ru(OH)x on La2O3 support was suitable for oxidation in is evident with the addition of copper to gold, compared with their
IL 1-ethyl-3-methylimidazolium acetate ([EMIM][OAc]), affording monometallic analogs (Table 6, Entries 2023). Moreover, bimetal-
an FDCA yield of 48% (Table 6, Entry 12). In comparison with other lic goldcopper nanoparticles supported on TiO2 are more active for
ILs such as [EMIM]Cl, [BMIM]Cl, [BMIM][PF6], [BMIM][BF4], and the oxidation of HMF to FDCA than Au/TiO2 and Cu/TiO2, which might
[EMIM][HSO4], [EMIM][OAc] appears to possess a higher solubili- be the result of gold site isolation caused by alloying. The stabili-
ty for oxygen, but rapidly degrades HMF [555], which renders it to zation effect and catalytic performance of the alloy are strongly
be the best IL solvent among those studied for this catalytic process. related to the amount of copper, and the highest level of reusabil-
Besides ruthenium containing catalysts, gold particles sup- ity and the best catalytic activity are obtained with the bimetallic
ported on metal oxides are promising catalysts for oxidation system of 1.5 wt% AuCu/TiO2 at Au/Cu atomic ratios of 1 and 3, re-
reactions. In the presence of a base promoter (e.g., NaOH or KOH), spectively [557]. Signicant synergistic effects have been observed
the oxidation of aqueous HMF occurs with a commercial hetero- between two alloyed metals for the base-free oxidation of HMF to
geneous Au/TiO2 catalyst, giving an FDCA yield of 71% (Table 6, Entry FDCA in AuPd/CNT (carbon nanotube; Table 6, Entries 2426) [492]
13) [487]. The Cannizzaro reaction along with favorable reaction con- and AuCu/CeO2 (Table 6, Entries 27 and 28) [493].
ditions for HMF degradation seems to be the reason why high the Both catalyst site basicity and type of oxidant are important to
FDCA yields are obtained. Compared with Au/TiO2, Au/Fe2O3 and Au/ selectively and eciently oxidize HMF to FDCA. The roles of added
C, Casanova et al. [488] found that Au/CeO2 displays a relatively base and molecular oxygen in the formation of FDCA from HMF with
higher catalytic activity for the aerobic oxidation of HMF-to-FDCA Pt/C or Au/TiO2 catalyst have been investigated through labeling ex-
in water than other Au/supports and gives and a maximum FDCA periments with 18O2 and H218O [558] (Fig. 26): (1) initial nucleophilic
yield of 100% (Table 6, Entries 1417). The nanoparticulate ceria addition of a hydroxide ion to the carbonyl group with the subse-
support with gold nanoparticles is possibly responsible for the ac- quent proton transfer from water gives a geminal diol; (2) the
celerated reaction rate, while the increased amount of Ce3+ from the carboxylic acid formed from dehydrogenation of the geminal diol
reductive pretreatment of Au/CeO2 catalyst probably enhances its intermediate is facilitated by the hydroxide ions adsorbed onto the
catalytic reactivity. The reaction mechanism proposed (Fig. 25), and metal surface; (3) the hydroxide ions further assist the activation
the alcohol oxidation of 5-hydroxymethyl-2-furancarboxylic acid of CH bond of the alcohol side-chain to afford HMFCA (aldehyde
(HMFCA) to FDCA was speculated to be the rate-limiting step. In intermediate); (4 and 5) the aldehyde side-chain of HMFCA is oxi-
the proposed reaction pathway (Fig. 25), HMFCA is initially formed dized to produce FDCA, analogous to the oxidation of HMF to HMFCA
from HMF via rapid oxidation of the intermediate Hemiacetal 1, in steps (1) and (2). Molecular oxygen is proposed to scavenge the
while the oxidation of HMFCA to 5-formyl-2-furancarboxylic acid electrons deposited into the metal particles so as to close the cata-
(FFCA) is slow, and then in situ generates the second hemiacetal in- lytic cycle, preferable to directly participating in oxidation or
termediate (Hemiacetal 2), which is rapidly converted into FDCA. dehydrogenation steps. Under identical conditions, platinum par-
Desorption of the acid product from the gold surface with a base ticles show higher selectivity for FDCA during HMF oxidation than
seems to be always required for the oxidation of HMF [556]. Then, gold, which might be attributed to the platinum being able to ac-
neutralization of the produced salts of carboxylic acid products with tivate the geminal hydrogen atoms of alcohol. Comparison of the
a homogeneous base is necessary at the end of the reaction. In this rate and product distribution in the oxidation of HMF to FDCA over
regard, solid base catalysts appear to be promising candidates for Pt/C, Pd/C, Au/C and Au/TiO2 shows the reactivity of platinum, pal-
the reaction. Gold supported on HT with moderate basicity facili- ladium and gold particles (Table 6, Entries 2932) [494] for which
tates the formation of FDCA that exceeds Au/TiO2, and 99% selectivity the rate of HMF oxidation to the intermediate HFCA with gold cat-
of FDCA at HMF conversion of 100% is obtained at 90 C in 20 h alyst is an order of magnitude higher than that with either platinum
(Table 6, Entry 18) [489]. Unfortunately, extensive leaching of mag- or palladium catalyst, while FDCA is directly formed by further ox-
nesium from HT results in the formation of a homogeneous basic idation of HFCA over platinum, palladium except gold particles. For
solution. By using the same catalyst Au/HT, Gupta et al. [490] de- Au/TiO2, the formation of FDCA from HFCA is realized under rela-
tected that gold species do not leach out of the HT support as tively higher O2 partial pressures (ca. 2000 or 3000 kPa) and base
conrmed by ICP analysis, and the catalyst eciently promotes HMF concentrations (ca. 2.0 M) in which the base concentration has a
H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194 137

Fig. 26. Overall reaction pathway for HMF (5-hydroxymethylfurfural) oxidation in aqueous solution (H218O) in the presence of dioxygen (18O2), excess base (OH) and either
platinum or gold catalyst. Adapted with permission from Ref. 558, Copyright 2011 Royal Society of Chemistry.

stronger effect on the reaction than the O2 partial pressure [494]. solutions, high yields of FDCA, fast rates, and good product solu-
For example, the selectivity for FDCA over Au/TiO2 increases from bilities are attained (Table 6, Entry 41), while reactions in neutral
3% to 28% when O2 partial pressure is increased from 690 to 2000 kPa solutions are slower and generally produce both DFF and FDCA
at 50% HMF conversion in 0.3 M NaOH solution, while 80% FDCA (Table 6, Entry 42). The product distribution of HMF oxidation can
selectivity and 100% HMF conversion are achieved in the presence be controlled to some extent by adjusting the acidbase proper-
of 2 M NaOH under 2000 kPa O2 partial pressure. ties of the reaction solution, which is possibly useful in practical
Saha et al. [495] aerobically oxidized HMF in acetic acid (HOAc) processes.
with Co(OAc) 2 /Zn(OAc) 2 /Br homogeneous catalyst, but 2,5- Krger et al. [497] converted fructose directly into FDCA in a two-
diformylfuran (DFF) is the only oxidation product with high yield phase system composed of water and MIBK, in which a microporous
(ca. 96%) (Table 6, Entry 33). When 1 wt% triuoroacetic acid (HTFA) cationic ion exchanger in H+ form (Lewatit SPC 108) catalyzes the
is added together with HOAc as acid additive, HMF is directly oxi- dehydration of fructose to HMF in the aqueous phase and a sub-
dized to FDCA with a maximum yield of 60% and FFCA (29% yield) sequent oxidation reaction occurs in the MIBK phase with a MIBK-
(Table 6, Entry 34). Supported catalysts Au/TiO2 and Au/CeO2 improve modied PtBi/C catalyst encapsulated in silicone beads. With this
HMF conversions from 62% to 84% and 29% to 83%, respectively, with catalytic system, a moderate FDCA yield of 25% is obtained at 80 C
corresponding FFCA yields increasing from 45% to 79% and 17% to at the end of the in situ oxidation process (Table 6, Entry 43). A bi-
71% in the absence and presence of 1 wt% HTFA (Table 6, Entries functional acidic and redox catalyst prepared by encapsulation of
3538). Among these Au/support catalysts, Au/TiO2 has a higher gold cobalt acetylacetonate into a solgel silica matrix is highly e-
content and BET surface area than Au/CeO2, which probably con- cient for direct fructose-to-FDCA conversion (Table 6, Entry 44) [498].
tributes to its higher catalytic activity. Extraction purication [559] in a triphasic system consisting of tet-
Lilga et al. [496] investigated the effect of basic, neutral, and acidic raethylammonium bromide (TEAB) or waterMIBKwater [560]
feeds on HMF oxidation. FDCA has low solubility in water (0.086 allows an integrated process for cascade dehydration and oxida-
wt% at 25 C), but has moderate solubility in carboxylic acid sol- tion of fructose in a single pot, affording an overall FDCA yields of
vents (e.g., for aqueous 40 vol% acetic acid, FDCA solubility is 0.153 83% and 78%, respectively, for those solvent systems.
wt% at 25 C). In acidic solutions, DFF is the preferred product with A few other catalytic systems have been proposed for the se-
about 70% selectivity over Pt/ZrO2 at 100 C using air as oxidant lective oxidation of HMF to FDCA. A highly cross-linked and thermally
(Table 6, Entry 39). By increasing the temperature from 100 to 140 C stable Fe3+-porous organic polymer (Fe3+-POP-1) containing basic por-
and introducing O2 instead of air, HMF conversion rises to 100% and phyrin subunits and iron metal center is an ecient heterogeneous
FDCA selectivity increases to 85% (Table 6, Entry 40). With basic catalyst for HMF oxidation, and a FDCA yield of 79% at HMF
138 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

Fig. 27. One-pot synthesis of DFF (2,5-diformylfuran) from glucose via successive isomerization, dehydration, and selective oxidation. Adapted with permission from Ref.
515, Copyright 2011 American Chemical Society.

conversion of 100% is obtained (Table 6, Entry 45) [499]. Merrield activated carbon supported Ru shows superior reactivity in the syn-
resin supported Co(II)meso-tetra(4-pyridyl)-porphyrin with tert- thesis of DFF from HMF.
butyl hydroperoxide as oxidant converts 96% HMF to yield 90% FDCA The effect of toluene, benzotriuoride, 1,4-dioxane, H2O, DMSO
(Table 6, Entry 46) [500]. Pd nanoparticles stabilized by PVP (poly- and N,N-dimethylformamide solvents on HMF-to-DFF conversion
vinyl pyrrolidone; Table 6, Entry 47) [501], Pt/-Al2O3 (Table 6, Entry for of Ru/C catalyst has been studied (Table 6, Entries 8286) [512].
48) [502], Li2CoMn3O8 (Table 6, Entry 49) [503], Pt/TiO2 and Pt/ Among the solvents, benzotriuoride has comparable activity with
ZrO2 (Table 6, Entries 50 and 51) [504] afford FDCA in high yields toluene (79.4 h1 vs. 61.2 h1) for almost the same DFF selectivity (95
from HMF. The properties of the supports affect both reactivity and %). In 1,4-dioxane solvent, Ru/C catalyst has high activity (74.8 h1)
stability of the metal nanoparticles in a direct way. In an external but low DFF selectivity (40 %), while water has a higher activity
magnetic eld, solid catalysts being paramagnetic and oxidizable, (160.7 h1) with moderate DFF selectivity (84%). Solvents N,N-
such as nano-Fe3O4CoOx, -Fe2O3@HAPPd and Pd/C@Fe3O4, are dimethylformamide and DMSO exhibit poor activities of 4.4 and
stable, magnetically separable, and active for HMF-to-FDCA oxida- 1.9 h1, respectively. The Ru0 species on Ru/C (61.2 h1) is more active
tion (Table 6, Entries 5254) [505507]. for HMF oxidation than that on RuOx/C (48.9 h1) and RuCl3/C
(29.3 h1) under identical conditions, and DFF selectivities of ~96%
4.1.2.2. 2,5-Diformylfuran (DFF). Synthesis of DFF from the oxida- are achieved over Ru/C [512]. Ru/C characterized by XPS (X-ray pho-
tion of the primary hydroxyl group in HMF without affecting the toelectron spectroscopy) shows the dominant presence of metallic
more reactive ,-unsaturated aldehyde group is a challenging route Ru0 particles with no essential change (76.5% vs. 75.6% Ru0) before
for fabricating macrocyclic ligands, pharmaceuticals, and function- and after the oxidation of HMF, demonstrating the Ru/C catalyst is
al materials [561563]. One of the rst representative studies on stable and recyclable under the reaction conditions.
the aerobic oxidation of HMF to DFF used homogeneous metal/ It is desirable to replace a two-step process that produces DFF
bromide catalysts (Co/Mn/Br and Co/Mn/Zr/Br) and was reported from carbohydrates through sequential dehydration and oxida-
by Partenheimer and Grushin (Table 6, Entries 55 and 56) [508]. tion reactions with a one-step process [564]. Xiang et al. [513]
When copper and vanadium immobilized in poly(4-vinylpyridine) developed a one-pot, one-step approach for direct conversion of
are crosslinked with 33% divinylbenzene (DVB) or supported on glucose to DFF with a catalytic system consisting of CrCl36H2O/
organofunctionalized SBA-15 mesoporous materials, relatively higher NaBr//NaVO32H2O. The two-step process gives higher DFF yields
activity and better chemoselectivity were observed, as compared (55%; Table 6, Entry 87) than the one-step process (18%). Yang et
with the corresponding homogeneous catalysts (Table 6, Entries 57 al. [514] examined the direct synthesis of DFF from fructose by suc-
62) [509]. Among these heterogeneous catalysts, vanadium- cessively using a solid acid Fe3O4SBASO3H and an oxygenant
containing polymeric catalysts are more active than their copper KOMS-2 (H0.2K0.8Mn8O16nH2O, octahedral molecular sieve) in a
analogs and afford DFF selectivities greater than 99% for 82% HMF single pot. Both catalytic processes are complementary to each other,
conversions (Table 6, Entry 61). However, metal leaching occurs in which Fe3O4SBASO3H is able to dehydrate fructose to HMF with
during the reaction. In contrast, SBA-15 mesoporous silica immo- a yield of 81%, while KOMS-2 promotes the successive oxidation
bilized pyridine-VO(acac)2 is able to avoid metal leaching, but its of HMF to produce DFF with a 99% yield and 100% selectivity (Table 6,
catalytic activity is far lower, with a maximum DFF selectivity of Entry 88). The catalytic system when used for the transformation
98% at HMF conversion of 50% (Table 6, Entry 62). To further improve of glucose and inulin to DFF gives low to moderate DFF yields
the reactivity of vanadium catalysts, partial substitution of VO3+ with (Table 6, Entries 89 and 90). When a combination of HT, Amberlyst-
different metal cations (Fe3+, Cr3+, Ga3+, Mg2+, Cu2+ and Pd2+) can be 15, and Ru/HT catalysts via stepwise addition was used for the
used (Table 6, Entries 6368) [510], however, no signicant im- successive isomerization, dehydration, and selective oxidation in one
provement in the catalytic performance is observed. Different metal pot (Fig. 27), an improved DFF yield of 25% is obtained from glucose
oxide supports including TiO2, Al2O3, Nb2O5, ZrO2, and MgO have been (Table 6, Entry 91) [515].
employed to immobilize VOx catalysts at varying VOx surface den- Several approaches to simplify the catalytic system for synthe-
sities (Table 6, Entries 6973) [511], and the support surfaces covered sis of DFF deserve to be mentioned. Impregnation of silver in
with acidity, polyvanadates and V2O5 clusters are demonstrated to KOMS-2 not only improves the activity by increasing the concen-
favor the formation of DFF. V2O5 clusters appear to show superior tration of basic sites and decreasing acidic sites, but also lowers the
activity to VO3+ species in the oxidation of HMF to DFF, and both required temperature of the reaction [516] (Table 6, Entry 92). Ru-
catalytic systems are likely to be promoted by acidic supports. thenium supported on activated carbon (Ru/C) eciently catalyzes
The inuence of supports, solvents, and metal oxidation states the oxidation of HMF to DFF with high selectivity and the product
on the activity and DFF selectivity of ruthenium catalysts has been distribution can be varied by adding water and HT, giving either FFCA
examined to understand structural requirements of immobilized or FDCA as the dominant product (Table 6, Entries 9396) [517]. Pro-
metal catalysts [512]. Solid supports including activated carbon, motion effects by Cu(NO3)2 on VOSO4-catalyzed aerobic oxidation
typical solid bases Mg2AlOx and MgO, solid acids Al2O3 and ZSM-5, for transforming HMF to DFF in acetonitrile reveals that the acti-
and amphoteric and redox oxides TiO2, CeO2, and ZrO2 have been vation of VOSO4 occurs to generate active V5+ species that effectively
adopted to support Ru (Table 6, Entries 7481). The weak acidity inhibit the oxidative CC bond cleavage of HMF and suppresses
and basicity in the supports promote DFF formation, and in particular, radical reactions of DFF that form humins (Table 6, Entry 97) [518].
H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194 139

Fig. 28. Proposed reaction pathway for the oxidation of HMF (5-hydroxymethylfurfural) over VO(acac)2. Adapted with permission from Ref. 538, Copyright 2011 Royal
Society of Chemistry.

As vanadyl (VO2+) and cupric (Cu2+) are immobilized on sulfonated -hydroxy ketone forms on the other side via resonance and is oxi-
carbon, the resulting catalyst with 0.93% V and 0.26% Cu exhibits dized to MA as the dominant product (Fig. 28, Route b). Although
the best performance (Table 6, Entry 98) among catalysts in this DFF is stable against further oxidation into FDCA or MA, the HMF
group (Table 6, Entries 97 and 98) [519]. The trimetallic mixed oxide can react with HCOOH formed in Route b, giving the methyl ester.
RuCo(OH)2CeO2 (Table 6, Entry 99) [520], acidic cesium salt of In acetonitrile/acetic acid solvent, control experiments with
molybdovanadophosphoric HPA Cs3HPMo11VO40 (Table 6, Entry 100) vanadium-substituted HPA H5PV2Mo10O40xH2O catalyst reveal that
[521], Cs0.5H2.5PMo12 (Table 6, Entry 101) [522], manganese oxide DFF, FFCA, FDCA and HMFCA do not appear in the pathway of MA
catalysts (Table 6, Entry 102) [523], protonated graphitic carbon formation (Table 6, Entry 119), despite some of these being iden-
nitride g-C3N4(H+) (Table 6, Entry 103) [524], vanadium supported tied in product analyses [539]. Thereby, the oxidation is veried
on activated carbon (V 2 O 5 /AC), polymers and zeolites (V 2 O 5 / to be initiated by the CC bond cleavage between the furan and
zeolite; Table 6, Entries 104106) [525527], N-hydroxyphthalimide/ hydroxymethyl group of HMF.
Cu(NO 3 ) 2 (Table 6, Entry 107) [528], 1-hydroxybenzotriazole/ Furfural can be used instead of HMF as the starting material to form
copper(I) iodate (Table 6, Entry 108) [529], ruthenium complex MA via homogeneous or heterogeneous catalysis. For instance, Yin et
immobilized on poly(4-vinylpyridine)-functionalized carbon- al. [540,541] reported that copper(II) nitrate in combination with phos-
nanotube (Table 6, Entry 109) [530], ruthenium clusters supported phomolybdic acid or H3PMo12O40xH2O affords MA with around 50%
on covalent triazine frameworks (Table 6, Entry 110) [531], 5 wt% yields from aerobic oxidation (Table 6, Entries 120 and 121). In the dom-
Pd-V(3:2)@MIL-101 (Table 6, Entry 111) [532], and even HBr/ inant oxidation pathway, the abstraction of hydrogen from the 5-position
DMSO or NaBr/DMSO (Table 6, Entry 112) [533] are ecient for the of furfural initiates the reaction and subsequently yields MA and
synthesis of DFF from HMF or sugars. A series of magnetically re- 5-acetoxyl-2(5H)-furanone [568]. Alonso-Fagndez et al. [542] used
cyclable catalysts including Mn3O4 (Table 6, Entry 113) [534], TEMPO VOx/Al2O3 solid catalyst for upgrading furfural by selective gas phase
(Table 6, Entry 114) [535], and ruthenium (Table 6, Entries 115 and oxidation to obtain MA in 73% yield for 100% furfural conversion (Table 6,
116) [536,537] supported on Fe3O4 nanoparticles are active for Entry 122). In the oxidative upgrading process, furfural is oxidized suc-
aerobic oxidation of HMF into DFF with many yields shown being cessively to furan and 2-furanone that is followed by rapid oxidative
more than 80%. As a common characteristic, redox sites as well as dehydration to give MA (Fig. 29). Relatively high MA yields are ob-
the promoting sub-units such as acidity/basicity, reaction media, tained from furfural using H2O2 as oxidant and titanium silicalite (TS-
catalyst structure and texture are involved in these catalytic systems, 1) as catalyst (Table 6, Entries 123 and 124) [543]. Ghaznavi et al. [544]
thus, synergistic actions may be present in the oxidative processes. used a catalytic process at high temperatures to atomize a xylose
water solution into a capillary uidized bed containing vanadyl
4.1.2.3. Maleic anhydride. Maleic anhydride (MA), which is pro- pyrophosphate catalyst. Compared with molybdenum trioxide
duced via selective oxidation of petroleum-based feedstocks at high cobalt oxide and iron molybdate, vanadyl pyrophosphate exhibits
temperatures (e.g., 400 C), is a versatile intermediate for 1,4- relatively higher activity (Table 6, Entries 125127). The surface density
butanediol, fumaric acid, unsaturated polyester resins, and THF of vanadium and molybdenum along with characteristics of the sup-
[565567]. Du et al. [538] explored a potential route to prepare MA ports probably affect the electronic properties and catalytic properties
from biomass derivatives using VO(acac)2 in acetonitrile and found of the supported metallic species.
that HMF is mainly oxidized into DFF (Fig. 28, Route a) and the MA
yield can be signicantly enhanced by increasing oxygen partial pres- 4.1.3. Oxidation of biomass derivatives to other oxygenates
sure (Table 6, Entries 117 and 118). The CC bond adjacent to the 4.1.3.1. 2,5-Dimethylfuroate (FDMC) and methyl furoate (MFA). An
hydroxymethyl group is easily broken and apparently, the second analog to FDCA is 2,5-dimethylfuroate (FDMC), which can be
140 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

Fig. 29. Possible reaction pathway for the oxidation of furfural to MA (maleic anhydride) over VOx/Al2O3.

synthesized from HMF dissolved in methanol via oxidation 4.1.3.2. FDCA-, DFF- and PBF-based polymers. FDCA- and DFF-
esterication in the presence of Au/TiO2 catalyst aided by CH3ONa based polymers can be synthesized from HMF or furfural via
(Table 6, Entry 128) [545]. The possible reaction route involves initial multistep reactions [570]. Pan et al. [570] prepared poly(butylene
oxidation of the aldehyde moiety of HMF to yield 5-hydroxymethyl 2,5-furandicarboxylate) (PBF) starting from furfural through a four-
methylfuroate (HMMF) in a high yield of ca. 90% under mild con- step synthetic sequence including nanoscale CuO catalyzed oxidation
ditions (0.1 MPa O2, 22 C and 1.5 h), and then formation of methyl of furfural into furoate (93% yield); catalytic disproportionation of
5-formyl-2-furoate (MFF) by oxidation of the hydroxymethyl group furoate to furan and FDCA (86% selectivity) with ZnCl2; and poly-
to the aldehyde, followed by the same oxidationesterication merization of FDCA with 1,4-butanediol (1,4-BDO), which was pre-
process to afford FDMC with 98% yield at a high temperature of synthesized with 70% selectivity through hydrogenation and
130 C and 0.4 MPa in 3 h (Fig. 30) Methyl furoate (MFA), which is hydrolysis of furan over ReRu/C, to produce polyester PBF with
used in avors and fragrances, can be produced from furfural through total carbon utilization of furfural (Fig. 32). Several other related syn-
the same catalytic process (Fig. 30). thetic routes have been put forward based on FDCA. For example,
Nanoparticulate CeO2 is able to adsorb oxygen due to its large the catalytic polytransesterication of FDCA with ethylene glycol
number oxygen vacancies. Moreover, the Lewis acid character of non- (EG) and 1,4-butylene glycol (BG) affords furan-based copolyesters
fully saturated cerium atoms is favorable for alcohol oxidation and using Ti(OC4H9)4 as catalyst [571]. Polyethylene furandicarboxylate
stabilization of positive metal particles. Casanova et al. [569] em- (PEF) formed via the polymerization of FDCA with EG is a promising
ployed Au/CeO2 solely as catalyst without base additive for the candidate to replace fossil fuelderived polyethylene terephthal-
synthesis of FDMC and MFA to obtain >99% selectivity for FDMC from ate (PET) [572], especially since the synthesis of poly(2,5-furan
HMF with >99% conversion, as well as 91% selectivity of MFA for dicarboxylate)s has been realized from diols [573].
furfural at a conversion of >99% (Table 6, Entries 129 and 130). Ca- Besides FDCA, DFF as a partially oxygenated compound with two
sanova et al. [569] proposed a reaction network (Fig. 31): both aldehyde groups also shows great potential in production of bio-
compounds 2 and 3 are derived from the same hemiacetal inter- polymers. A series of porous furan-based organic frameworks (FOF)
mediate 1 though successively dominant oxidation and subordinate have been prepared by condensation of DFF with diamines through
acetalization reaction to provide compound 4 in two separate path- the formation of imine linkages without the presence of catalyst
ways, and the resulting monoester acetal is further oxidized into [574]. The condensation of monomer DFF with urea at 110 C by
the diester FDMC. When Au/ZrO2 is employed as catalyst, oxida- melting a solid mixture can give a crystalline polymer resin in 90%
tive esterication of furfural proceeds under mild conditions, giving yield [575].
almost complete selectivity to methyl-2-furoate, while oxygen partial
pressures lower than 0.1 MPa do not signicantly affect the cata- 4.1.3.3. Succinic acid and 3-hydroxypropanoic acid from levulinic
lytic performance for either system (Table 6, Entries 131133) [546]. acid. Levulinate derivatives are readily produced from lignocellu-
Catalytic activities for the oxidative esterication of furfural and HMF losic carbohydrates. Podolean et al. [549] found that Ru-based
have the following trends: Au/ZrO2 > Au/CeO2 Au/TiO2, for which magnetic nanoparticles are ecient for the oxidation of LA to suc-
the surface area of the supports and surface sites (e.g., 2 wt% nominal cinic acid (96% selectivity) (Table 6, Entry 140), in which strong
sulfate content) separately affect conversions and the selectivities Bronsted acid sites are responsible for catalyzing the oxidation of
(Table 6, Entries 134139) [547,548]. the carbon backbone of LA via a BaeyerVilliger (BV) mechanism.

Fig. 30. Biomass sugar feedstock transformed into 2,5-dimethylfuroate (FDMC) and methyl furoate (MFA) via oxidationesterication.
H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194 141

Fig. 31. Proposed oxidationesterication pathway starting from 5-hydroxymethylfurfural (HMF). Adapted with permission from Ref. 569, Copyright 2009 Elsevier.

Choudhary et al. [550] demonstrated that the use of a strong with strong Bronsted acids like p-TsOH, MeSO3H, H2SO4, TfOH, and
Bronsted acid Amberlyst-15 and 30% aqueous H2O2 catalyzes the Amberlyst-15 (Table 6, Entries 142149). Lewis acidic triate salts
oxidation of LA to SA (Table 6, Entry 141). By changing the solvent are active for the oxidation of ML, and the metal cation inuences
from water to methanol, Wang et al. [551] found that selectivities the reaction selectivity. The succinate/acetate ratio decreases from
to methyl succinate and methyl acetate of around 60 and 40%, re- 1.6 to 0.3 as the solvent is switched from methanol to heptane, and
spectively, are obtained from methyl levulinate (ML) in aqueous H2O2 the higher degree of branching in the carbon backbone caused by

Fig. 32. Multiple conversion of furfural into FDCA (2,5-furandicarboxylic acid)-based polyester PBF [poly(butylene 2,5-furandicarboxylate)]. Adapted with permission from
Ref. 570, Copyright 2013 Wiley-VCH.
142 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

Fig. 33. BaeyerVilliger oxidation of LA (levulinic acid) to SA (succinic acid) and 3-hydroxypropanoic acid. Adapted with permission from Ref. 552, Copyright 2015 Wiley-VCH.

methanol is thought to result in a high molar ratio of methyl suc- biomass with bifunctional solid materials has the potential to sim-
cinate and acetate (up to 1.6:1) Either CH3 or CH2CH2COOH, plify pretreatment, intermediate separation, and post-treatment steps
migration in the oxidation of LA occurs such that the dominant required for producing chemical products. However, only a limited
product can be selectively xed to SA or 3-hydroxypropanoic acid number of one-pot oxidation examples have been reported, indi-
(Table 6, Entries 150 and 151) [552], as illustrated in Fig. 33. Under cating the infancy of this topic in the eld. Nevertheless, increasing
acidic conditions in 30% aqueous H2O2, direct treatment of LA gives research into bifunctional solid catalytic systems is certain to allow
predominantly SA [553], while 3-hydroxypropanoic acid is ob- clear examples to be developed in the near future.
tained from LA via an intermediate 3-(hydroperoxy)propanoic acid
under basic conditions proceeds through a two-step catalytic process 4.2. Production of hydrogenates
involving partial oxidation with H2O2 at 0 C to room temperature
and subsequent hydrogenation reaction over Pd/C [552]. The proper Catalytic dehydration, esterication, etherication and
adjustment of pH appears to be a key factor in controlling the product acetalization over functional materials are used to convert sugars,
distribution, even though conditions of the catalytic system must glycerol, LA, furans and fatty acids into fuel additives, whereas
be chosen to suppress the formation of byproducts. biomass-derived liquid hydrocarbon fuels are obtained by combin-
ing oxygen removal processes such as hydrogenolysis, hydrogenation
4.1.3.4. a-Conidendrin (Coni) and a-conidendric acid (ConiA) from and decarbonylation with CC coupling reactions including aldol
lignans. Lignans, which are a group of phenolic compounds pos- condensation, hydroxyalkylation, oligomerization and ketonization
sessing anti-carcinogenic and anti-oxidative properties, can be to adjust the molecular weight of platform molecules [590,591]. In
applied to cosmetic and pharmaceutical products [576]. Among these this section, an overview of catalytic processes that use deoxygen-
phenolic chemicals, oxomatairesinol (oxoMAT) can be synthe- ation of biomass derivatives is presented and bifunctional material-
sized from hydroxymatairesinol (HMR) via oxidation of its secondary mediated reaction pathways are emphasized.
alcohol group over supported palladium and gold catalysts
[577579]. Both isomers HMR 1 and HMR 2 can be oxidized to 4.2.1. Hydrolysishydrogenation of bio-polymers to polyols
oxoMAT with the major contaminants of -conidendrin (Coni) and Hexitols, which are considered as important platform chemi-
-conidendric acid (ConiA) over Au/Al2O3 catalysts in a basic solu- cals for the production of H2, liquid alkanes, and value-added
tion at 70 C and atmospheric pressure (Fig. 34) [580]. The maximum chemicals such as sorbitan, isosorbide, glycerol and lactic acid, can
activity of supported gold catalysts corresponds to an Au particle be derived from polysaccharides [592594]. Pretreatment/hydrolysis
diameter of 4 nm. In addition to the acidbase properties of solid steps are generally required to overcome the recalcitrance of lig-
supports and reaction media, the morphological structures of metal nocelluloses, for which bifunctional catalytic systems have shown
particles, such as degree of dispersion and particle size, affect the great promise in the successive hydrolysishydrogenation reac-
performance of the bifunctional materials. tions to afford sorbitol and mannitol (Fig. 35) [595]. In an acidic
Lignin, which is a complex aromatic polymer that is widely- solution (pH = 2), Ru nanoclusters promote quantitative produc-
dispersed in nature, has great potential for producing engineering tion of sorbitol (100% yield) from cellobiose at 120 C and 4 MPa
plastics and thermoplastic elastomers, low-cost carbon bers, fun- H2 partial pressure, while low yields of sorbitol are obtained under
gible fuels, polymeric foams, and commodity chemicals [581]. neutral or basic conditions (pH = 7 or 10; Table 7, Entries 13) [596].
Hydrothermal gasication, wet oxidation and hydrothermal lique- The direct conversion of cellobiose into sorbitol under a hydrogen
faction convert lignin to fuel gas, aromatic aldehydes and phenolic atmosphere has been achieved with acid-modied carbon nanotube
products, respectively [582584], while integrated pretreatment with (CNT)-supported ruthenium catalysts in neutral water (Table 7, Entry
subsequent valorization is necessary for developing lignin-to- 4) [597]. The presence of H2O in Ru/CNT renders the formation of
bioproduct processes [585589]. One-pot catalytic oxidation of oxygen-containing groups and uniform defects on the tube-walls,
H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194 143

Fig. 34. Schematic of converting the lignan hydroxymatairesinol (NMR) to -conidendrin (Coni) and -conidendric acid (ConiA) over gold catalysts. oxoMAT: oxomatairesinol.
Adapted with permission from Ref. 580, Copyright 2015 Elsevier.

resulting in the highly stable and dispersed Ru nanoparticles, as well Apart from Ru nanoparticles, some other supported metal
as higher yields of sugar alcohols (39%) and conversion of cellobi- nanoparticles such as Pt and Ni eciently convert cellobiose and
ose (74%) than Ru/CNT without water (21% and 29%, respectively; cellulose into sugar alcohols. Comparable yields of sugar alcohols
Table 7, Entries 58) [598,599]. (~25%) are obtained over -Al2O3 supported Pt catalyst (Table 7, Entry
If the substrate is changed from cellobiose to cellulose, carbon- 24) [612], while the acid sites for the hydrolysis of cellulose are gen-
supported Ru clusters together with in-situ generated [H+] ions in erated in-situ from H2 [631]. To enhance the anity between
hot water afford hexitols with a sorbitol/mannitol molar ratio of cellulose and catalyst, a brous three-dimensional (3D) carbon ma-
about 3.6/1 in a yield of 22% at 39% conversion under 6 MPa H2 partial terial mimicking the shape of a sea urchin (Echinometra mathae) has
pressure at 245 C in 5 min (Table 7, Entries 9 and 10) [600]. The been used to support Pt particles [613]. The resulting catalyst is very
catalytic performance of ZrP combined with commercial 5% Ru/C active for the hydrolysis of cellulose even though the support was
in hydrolytic hydrogenation of cellulose to sorbitol/mannitol has been not treated with [H+] species, affording hexitols in a total yield of
evaluated, and maximum sorbitol/mannitol yields of 62% and 81% ~80% (Table 7, Entry 25). Instead of hydrogen gas, the combined use
are obtained from microcrystalline and ball-milled cellulose, re- of carbon monoxide (CO)/H2O as a hydrogen source with PtMo2C/C
spectively (Table 7, Entry 11) [601]. Both the adsorbed hydrogen catalyst can promote the hydrolysishydrogenation of cellulose to
species concentrations and the acidic functional groups on the produce polyols in a yield of 42% with 60% selectivity to hexitols
support surfaces affect the sorbitol formation [629,630]. A great (Table 7, Entry 26) [614]. In this catalytic process, the PtMo2C
number of ruthenium-based catalysts have been studied for this re- domains are responsible for the formation of active hydrogen species
action. In particular, a sorbitol yield of 71% could be achieved from from the watergas shift reaction rather than from the CC bond
cellulose with Ru nanoparticles on carbon treated with sulfuric acid cleavage reaction, while the PtC domains mainly catalyze the
(Ru/ACSO3H) in a neutral aqueous solution (Table 7, Entry 12) [602]. succedent hydrogenation/hydrogenolysis reaction. In contrast, Ni
Other bifunctional catalysts such as Keggin-type polyoxometalates nanoparticles on aluminum hydroxide (Ni/AlOH) are more stable
loaded with ruthenium nanoparticles (Ru/Cs2HPW12O40 and Ru/ and active than pyrophoric Raney Ni in the two sequential reac-
[Bmim]3PW12O40; Table 7, Entries 13 and 14) [603,604], ruthenium tions, giving sugar alcohols in a total yield of 89% at a cellobiose
supported on a Beta and Y zeolite (Ru/Beta and Ru/Y; Table 7, Entries conversion of 90% (Table 7, Entries 27 and 28) [615]. The presence
1517) [605,606], mesoporous niobium phosphate (Ru/NbOPO4; of aluminum hydroxide causes a high dispersion of Ni metal species,
Table 7, Entry 18) [607] and arenesulfonic acid functionalized in particular, the NiNPs/AlOH catalyst is able to be reused at least
mesoporous silica (Ru/SBA15-SO3H; Table 7, Entry 19) [608], and ve consecutive cycles with almost no loss of activity (conversion
Bronsted acid-promoted ruthenium catalysts (e.g., Ru/C + MCM- rate) with selectivity successively decreasing from 99 to 98% and
41SO3H or ZrP; Table 7, Entries 2022) [609,610], as well as PTA/ >99 to 98% for sucrose hydrogenolysis. Notably, nickel-based bi-
metal-organic-framework-hybrid immobilized ruthenium catalyst metals on activated carbon (AC) or mesoporous carbon (MC) exhibit
(RuPTA/MIL-100(Cr); Table 7, Entry 23) [611] are ecient for the improved catalytic performance and stability in comparison with
sequential hydrolysis and hydrogenation of cellulose into sorbitol isolated metals such as Ir and Ni (Table 7, Entries 2938) [616], which
in neutral water under a hydrogen atmosphere. When the molar might be the result from tunable electronic and chemical proper-
ratio of acid sites to the number of Ru surface atoms (e.g., 8.84 ties of the bimetallic catalysts that are superior to those of the single
12.90) [611] has sucient density, hexitol yields reach a maximum metal particles [632,633]. Ni-containing carbon nanobers (Ni/
from di- and polysaccharide (e.g., cellobiose and cellulose) substrates. CNFs) synthesized through catalytic vapor deposition (CVD) of CH4
144 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

Fig. 35. Plausible reaction pathways for the conversion of cellulose to hexitols.

over Ni nanoclusters on -alumina afford a moderate yield of hexitols emerging from both hot H2O and the surface tungsten oxides or
(35%) from the degradation of microcrystalline cellulose with 87% phosphates act on cellulose hydrolysis, while WCx or WP with the
conversion (Table 7, Entry 39) [617]. Since Ni particles attach at the platinum-like electronic properties is responsible for the subse-
tip of the inert CNF (carbon nanober), the metal sites in the porous quent hydrogenation (Table 7, Entries 4749) [621,622]. For the case
supports are fully accessible. Anchoring and dispersing Ni precur- of a 3D mesoporous carbon (MC) supported WCx nanoparticles, the
sors onto CNFs can be realized by the oxidative activation of the CNFs 3D interconnected mesoporous structure of MC support is able to
with HNO3 [634636], and the acid strength/concentration of Ni/ facilitate the accessibility/dispersion of active component WCx and
CNF-catalysts can be adjusted by tailoring the preparation methods the transportation of molecules, thereby enhancing hydrogena-
[618]. Among various CNF-supported Ni particles, the Ni/CNFs with tion activity [638] and gives an EG yield of 73% (Table 7, Entries 50
a catalyst loading of 7.5 wt % prepared by chemical vapor deposi- 52) [623]. In contrast, tungsten and tungsten oxide species (e.g., WO3,
tion of CH4 on a Ni/-Al2O3 catalyst, followed by oxidation in HNO3 W, insoluble H2WO4, soluble HxWO3 and HPAs) are only active for
(twice for 1 h at 110 C), incipient wetness impregnation, and re- CC cleavage of cellulose, while an extra transition metal in the form
duction at 550 C under a H2 atmosphere are highly active for the of MW species is responsible for the subsequent hydrogenation
hydrolytic hydrogenation of cellulose, affording a maximum hexitols accessible to EG (Table 7, Entries 5368) [624627]. Xi et al. [628]
yield of 76% with 69% sorbitol selectivity and 93% cellulose con- reported that NbOPO4 as a support and catalyst can accelerate the
version (Table 7, Entries 4043). Properly balanced Ni/CNF catalysts cleavage of a CC bond while supported Ru particles are respon-
in terms of Ni dispersion, hydrogenation capacity, and the number sible for the further hydrogenation, so as to convert cellulose into
of acidic surfaceoxygen groups are likely to be responsible for the EG and EG monoether (EGME) in a total yield of 55% (Table 7, Entry
enhanced activity in hydrolytic hydrogenation of cellulose to hexitols. 69). The dopant Ni rather than W, Sn and Cu is more effective for
The cleavage of CC bonds of saccharides is eciently pro- the production of EG + EGME with a 64% total yield, which is prob-
moted by tungsten-based catalysts, yielding EG rather than hexitols ably because Ni can restrain the further hydrogenolysis of the
as the dominant product in the sequential hydrolysis and resulting products to byproducts such as CO and alkanes, while W,
hydrogenolysis of cellulose (Fig. 36; Table 7, Entries 4446) Sn, and Cu are all able to promote degradation of EG and EGME
[619,620,637]. Tungsten carbide (WCx) or tungsten phosphide (WP) (Table 7, Entries 7073). Therefore, appropriate combination of metal
without adding transition metal particles has the capability to species with acid sites is necessary for enhancing and controlling
produce EG directly from cellulose. In this catalytic process, [H+] the selectivity of polyols from carbohydrates involving multi-step
Table 7
Catalytic conversion of carbohydrates to polyols through cascade hydrolysis (Cat-1) and hydrogenation (Cat-2) with summary of reaction conditions, H-donor, maximum catalytic activity and catalyst reusability.

Entry Substrate Catalyst Reaction conditionb H-donor Main product Catalytic activity Reusability Ref.

Cat-1 Cat-2 Solvent Temp. Time Conv Yield Cycles Yieldc

1 Cellobiose (1.1 wt%) HCl (pH = 2) 0.7 mol%a Ru/PVP H2O 120 C 12 h 4.0 MPa H2 Sorbitol 100% 100% NMd NM [596]
[Glucose] [0]
2 Cellobiose (1.1 wt%) 0.7 mol% Ru/PVP H2O 120 C 12 h 4.0 MPa H2 Sorbitol 88% 23% NM NM [596]
(pH = 7) [Glucose] [1%]
3 Cellobiose (1.1 wt%) NaOH 0.7 mol% Ru/PVP H2O 120 C 12 h 4.0 MPa H2 Sorbitol 76% 18% NM NM [596]
(pH = 10) [Glucose] [2%]
4 Cellobiose (0.9 wt%) 1.0 wt% Ru/CNT pretreated with 68 wt% HNO3 H2O 185 C 3h 5.0 MPa H2 Sorbitol 100% 87% NM NM [597]
5 Cellobiose (0.9 wt%) 1.5 wt% Ru/CNT pretreated with H2O H2O 185 C 3h 5.0 MPa H2 Sorbitol 74% 39% NM NM [598]
6 Cellobiose (0.9 wt%) 1.5 wt% Ru/CNT without H2O pretreatment H2O 185 C 3h 5.0 MPa H2 Sorbitol 29% 21% NM NM [598]
7 Cellobiose (0.9 wt%) 2.0 wt% Ru-in-CNT pretreated with 68 wt% HNO3 H2O 185 C 3h 5.0 MPa H2 Sorbitol 60% 44% NM NM [599]
8 Cellobiose (0.9 wt%) 2.0 wt% Ru-in-CNT pretreated with 23 wt% HNO3 H2O 185 C 3h 5.0 MPa H2 Sorbitol 47% 35% NM NM [599]
9 Cellulose (2.0 wt%) In situ generated H+ 4 wt% Ru/C H2O 245 C 5 min 6.0 MPa H2 Sorbitol 39% 17% NM NM [600]
[Mannitol] [5%]

H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194


10 Cellulose (2.0 wt%) In situ generated H+ 4 wt% Ru/C H2O 245 C 30 min 6.0 MPa H2 Sorbitol 86% 30% NM NM [600]
[Mannitol] [10%]
11 Cellulose (10.0 wt%) 10 wt% ZrP 5 wt% Ru/C H2O 215 C 3h 6.0 MPa H2 Sorbitol + mannitol 99% 62% 4 57% [601]
12 Cellulose (10.0 wt%) 10 wt% Ru/ACSO3H H2O 140 C 36 h 5.0 MPa H2 Sorbitol 96% 71% 5 59% [602]
(24 h)
13 Cellobiose (1.0 wt%) 1.0 wt% Ru/Cs2HPW12O40 H2O 140 C 6h 2.0 MPa H2 Sorbitol 99% 93% 5 72% [603]
14 Cellulose (5.0 wt%) 5.0 wt% Ru/[Bmim]3PW12O40 H2O 160 C 24 h 5.0 MPa H2 Sorbitol 64% 45% NM NM [604]
15 Cellobiose (2.8 wt%) 3.0 wt% SnF4 3.0 wt% Ru/Beta H2O 180 C 3h 1.6 MPa H2 Sorbitol 99% 72% NM NM [605]
16 Glucose (2.8 wt%) 3.0 wt% Ru/Beta H2O 180 C 3h 1.6 MPa H2 Sorbitol 100% 73% NM NM [605]
17 Glucose (20 wt%) 1.0 wt% Ru/Y H2O 120 C 3h 5.5 MPa H2 Sorbitol 100% 99% 4 ~90% [606]
18 Cellulose (0.8 wt%) 5.0 wt% Ru/NbOPO4 H2O 170 C 24 h 4.0 MPa H2 Sorbitol 93% 60% 4 58% [607]
19 Cellulose (2.0 wt%) 4.0 wt% Ru/SBA-15SO3H H2O 110 Ce 1h 3.5 MPa H2 Sorbitol 39% 27% NM NM [608]
20 Cellulose (2.0 wt%) 3.0 wt% Ru/C H2O 230 C 40 min 6.0 MPa H2 Sorbitol 61% 46% NM NM [609]
[Mannitol] [7%]
(EG) (5%)
21 Cellulose (2.0 wt%) 100 wt% MCM-41SO3H 3.0 wt% Ru/C H2O 230 C 40 min 6.0 MPa H2 Sorbitol 100% 7% NM NM [609]
[Mannitol] [1%]
(EG) (49%)
22 Cellulose (1.0 wt%) 180 wt% ZrP 5.0 wt% Ru/C H2O 215 C 3.0 h 6.0 MPa H2 Sorbitol + 99% 64% 5 55% [610]
mannitol
23 Cellobiose (1.0 wt%) 3.2 wt% RuPTA/MIL-100(Cr) H2O 150 C 10 h 2.0 MPa H2 Sorbitol 100% 92% 2 9% [611]
[Mannitol] [5%] []
24 Cellulose (0.8 wt%) In situ generated H+ 2.5 wt% Pt/-Al2O3 H2O 190 C 24 h 5.0 MPa H2 Sorbitol 100% 25% 3 20% [612]
[Mannitol] [6%] [5%]
25 Cellulose (1.0 wt%) 5 wt% Pt/Echinometra mathae H2O 180 C 24 h 5.0 MPa H2 Sorbitol 96% 67% 3 56% [613]
[Mannitol] [12%] [11%]
26 Cellulose (0.8 wt%) 5 wt% PtMo2C/C H2O 240 C 30 min 4.5 MPa CO Sorbitol 22% NM NM [614]
[Mannitol] [4%]
27 Sucrose (2.4 wt%) 4.0 wt% Raney Ni H2O 130 C 24 h 2.0 MPa H2 Sorbitol 94% <1% NM NM [615]
[Mannitol] [84%]
28 Sucrose (2.4 wt%) 3.5 wt% Ni/AlOH H2O 130 C 24 h 2.0 MPa H2 Sorbitol 99% <1% 5 <1% [615]
[Mannitol] [95%] [93%]
29 Cellulose (1.0 wt%) 1 wt% Ir/AC H2O 245 C 30 min 6.0 MPa H2 Sorbitol 66% 2% NM NM [616]
[Mannitol] [1%]
30 Cellulose (1.0 wt%) 5 wt% Ni/AC H2O 245 C 30 min 6.0 MPa H2 Sorbitol 59% 6% NM NM [616]
[Mannitol] [2%]
31 Cellulose (1.0 wt%) 1 wt% Ir5 wt% Ni/AC H2O 245 C 30 min 6.0 MPa H2 Sorbitol 79% 8% NM NM [616]
[Mannitol] [5%]
32 Cellulose (1.0 wt%) 1 wt% Ir/MC H2O 245 C 30 min 6.0 MPa H2 Sorbitol 90% 4% NM NM [616]
[Mannitol] [1%]
(continued on next page)

145
146
Table 7 (continued)

Entry Substrate Catalyst Reaction conditionb H-donor Main product Catalytic activity Reusability Ref.

Cat-1 Cat-2 Solvent Temp. Time Conv Yield Cycles Yieldc

33 Cellulose (1.0 wt%) 5 wt% Ni/MC H2O 245 C 30 min 6.0 MPa H2 Sorbitol 86% 8% NM NM [616]
[Mannitol] [3%]
34 Cellulose (1.0 wt%) 1 wt% Ir5 wt% Ni/MC H2O 245 C 30 min 6.0 MPa H2 Sorbitol 100% 48% 5 45% [616]
[Mannitol] [10%] [5%]
35 Cellulose (1.0 wt%) 1 wt% Pt5 wt% Ni/MC H2O 245 C 30 min 6.0 MPa H2 Sorbitol 100% 40% NM NM [616]
[Mannitol] [8%]
36 Cellulose (1.0 wt%) 1 wt% Pd5 wt% Ni/MC H2O 245 C 30 min 6.0 MPa H2 Sorbitol 100% 48% NM NM [616]
[Mannitol] [6%]
37 Cellulose (1.0 wt%) 1 wt% Ru5 wt% Ni/MC H2O 245 C 30 min 6.0 MPa H2 Sorbitol 100% 42% NM NM [616]
[Mannitol] [13%]
38 Cellulose (1.0 wt%) 1 wt% Rh5 wt% Ni/MC H2O 245 C 30 min 6.0 MPa H2 Sorbitol 100% 52% NM NM [616]
[Mannitol] [8%]
39 Cellulose (2.0 wt%) 3.0 wt% Ni/CNFs H2O 210 C 24 h 6.0 MPa H2 Sorbitol 87% 30% NM NM [617]
[Mannitol] [5%]

H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194


40 Cellulose (2.0 wt%) 2.6 wt% Ni/CNFs H2O 190 C 24 h 6.0 MPa H2 Sorbitol 91% 40% NM NM [618]
[Mannitol] [9%]
41 Cellulose (2.0 wt%) 5.2 wt% Ni/CNFs H2O 190 C 24 h 6.0 MPa H2 Sorbitol 93% 58% NM NM [618]
[Mannitol] [11%]
42 Cellulose (2.0 wt%) 7.5 wt% Ni/CNFs H2O 190 C 24 h 6.0 MPa H2 Sorbitol 93% 64% NM NM [618]
[Mannitol] [12%]
43 Cellulose (2.0 wt%) 7.5 wt% Ni/CNFs H2O 190 C 24 h 6.0 MPa H2 Sorbitol 93% 53% NM NM [618]
[Mannitol] [11%]
44 Cellulose (1.0 wt%) 2.0 wt% NiW2C/AC H2O 245 C 30 min 6.0 MPa H2 EG 100% 61% NM NM [619]
[PG] [8%]
45 Corn stalk (1.0 wt%) 2.0 wt% NiW2C/AC H2O 245 C 2h 6.0 MPa H2 EG 96% 18% NM NM [620]
[PG] [14%]
46 Xylose (1.0 wt%) 2.0 wt% NiW2C/AC H2O 245 C 2h 6.0 MPa H2 EG 100% 11% NM NM [620]
[PG] [17%]
47 Cellulose (1.0 wt%) 2.0 wt% NiWP/AC H2O 245 C 30 min 6.0 MPa H2 EG 100% 46% NM NM [621]
[PG] [6%]
48 Cellulose (1.0 wt%) 10.0 wt% Ni/AC H2O 245 C 30 min 6.0 MPa H2 EG 74% 10% NM NM [621]
[PG] [5%]
49 Cellulose (1.0 wt%) 30.0 wt% W2C/AC H2O 245 C 30 min 6.0 MPa H2 EG 98% 27% 3 23% [622]
[PG] [6%] [3%]
50 Cellulose (1.0 wt%) 30 wt% WCx/MC H2O 245 C 30 min 6.0 MPa H2 EG 100% 73% 3 57% [623]
[PG] [5%] [8%]
51 Cellulose (1.0 wt%) 2 wt% NiWCx/MC H2O 245 C 30 min 6.0 MPa H2 EG 98% 27% 3 23% [623]
[PG] [6%] [3%]
52 Cellulose (1.0 wt%) 2 wt% NiWCx/AC H2O 245 C 30 min 6.0 MPa H2 EG 100% 62% NM NM [623]
[PG] [3%]
53 Cellulose (1.0 wt%) 10.0 wt% H2WO4 1.2 wt% Ru/AC H2O 245 C 30 min 6.0 MPa H2 EG 100% 54% 20 50% [624]
[PG] [6%] []
54 Cellulose (1.0 wt%) 10.0 wt% H2WO4 10.0 wt% Raney Ni H2O 245 C 30 min 6.0 MPa H2 EG 100% 65% 21 50% [625]
[PG] [3%] [5%]
55 Cellulose (1.0 wt%) 10.0 wt% WO3 10.0 wt% Raney Ni H2O 245 C 30 min 6.0 MPa H2 EG 100% 53% NM NM [625]
[PG] [2%]
56 Cellulose (1.0 wt%) 10.0 wt% H3PW12O40 10.0 wt% Raney Ni H2O 245 C 30 min 6.0 MPa H2 EG 100% 49% NM NM [625]
[PG] [5%]
57 Cellulose (1.0 wt%) 10.0 wt% H3SiW12O40 10.0 wt% Raney Ni H2O 245 C 30 min 6.0 MPa H2 EG 100% 35% NM NM [625]
[PG] [5%]
58 Glucose (0.3 wt%) 3.0 wt% Ru/C H2O 205 C 10 min 6.0 MPa H2 EG 100% 9% NM NM [626]
[PG] [6%]
(Sorbitol) (70%)
(continued on next page)
Table 7 (continued)

Entry Substrate Catalyst Reaction conditionb H-donor Main product Catalytic activity Reusability Ref.
c
Cat-1 Cat-2 Solvent Temp. Time Conv Yield Cycles Yield

59 Glucose (0.3 wt%) 1000 wt% WO3 3.0 wt% Ru/C H2O 205 C 10 min 6.0 MPa H2 EG 100% 59% NM NM [626]
[PG] [14%]
(Sorbitol) (9%)
60 Cellulose (1.0 wt%) 5 wt% PdW/AC H2O 245 C 30 min 6.0 MPa H2 EG 100% 60% NM NM [627]
[PG] [4%]
61 Cellulose (1.0 wt%) 5 wt% PtW/AC H2O 245 C 30 min 6.0 MPa H2 EG 97% 57% NM NM [627]
[PG] [3%]
62 Cellulose (1.0 wt%) 5 wt% RuW/AC H2O 245 C 30 min 6.0 MPa H2 EG 100% 62% NM NM [627]

H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194


[PG] [3%]
63 Cellulose (1.0 wt%) 5 wt% IrW/AC H2O 245 C 30 min 6.0 MPa H2 EG 100% 51% NM NM [627]
[PG] [3%]
64 Cellulose (1.0 wt%) 30 wt% W/AC H2O 245 C 30 min 6.0 MPa H2 EG 100% 2% NM NM [627]
[PG] [0]
65 Cellulose (1.0 wt%) 5 wt% Pd/AC H2O 245 C 30 min 6.0 MPa H2 EG 67% 8% NM NM [627]
[PG] [0]
66 Cellulose (1.0 wt%) 5 wt% Pt/AC H2O 245 C 30 min 6.0 MPa H2 EG 64% 12% NM NM [627]
[PG] [3%]
67 Cellulose (1.0 wt%) 5 wt% Ru/AC H2O 245 C 30 min 6.0 MPa H2 EG 74% 2% NM NM [627]
[PG] [0]
68 Cellulose (1.0 wt%) 5 wt% Ir/AC H2O 245 C 30 min 6.0 MPa H2 EG 64% 10% NM NM [627]
[PG] [7%]
69 Cellulose (3.8 wt%) 3 wt% Ru/NbOPO4 MeOH 220 C 20 h 3.0 MPa H2 EG 96% 26% NM NM [628]
[PG] [3%]
(EGMG) (29%)
70 Cellulose (3.8 wt%) 3 wt% Ru0.9 wt% W/NbOPO4 MeOH 220 C 20 h 3.0 MPa H2 EG 93% 20% NM NM [628]
[PG] [3%]
(EGMG) (23%)
71 Cellulose (3.8 wt%) 3 wt% Ru0.9 wt% Sn/NbOPO4 MeOH 220 C 20 h 3.0 MPa H2 EG 90% 13% NM NM [628]
[PG] [2%]
(EGMG) (25%)
72 Cellulose (3.8 wt%) 3 wt% Ru0.9 wt% Ni/NbOPO4 MeOH 220 C 20 h 3.0 MPa H2 EG 90% 20% NM NM [628]
[PG] [2%]
(EGMG) (40%)
73 Cellulose (3.8 wt%) 3 wt% Ru0.9 wt% Cu/NbOPO4 MeOH 220 C 20 h 3.0 MPa H2 EG 89% 11% NM NM [628]
[PG] [1%]
(EGMG) (25%)
a
Metal loading in the catalyst or solid acid dosage.
b Reaction conditions used for hydrodeoxygenation.
c Product yield in the last cycle.
d
NM: not mentioned.
e Irradiation at 300 W.

PVP: poly(N-vinyl-2-pyrrolidone), CNT: carbon nanotube, EG: ethylene glycol, PG: 1,2-propylene glycol, Ru-PTA/MIL-100(Cr): phosphotungstic acid (PTA)/metalorganic-framework-hybrid-supported ruthenium catalyst, AC:
activated carbon, MC: mesoporous carbon, CNFs: carbon nanobers (treated with HNO3), EGME: EG monoether.

147
148 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

Fig. 36. Schematic of catalytic conversion of cellulose to ethylene glycol (EG).

reactions such as hydrolysis, hydrogenation/hydrogenolysis, and CC 4.2.2.1. 2,5-Dimethylfuran (DMF). A two-step process involving the
bond cleavage. dehydration of fructose to HMF catalyzed by HCl in H2O/2-butanol
(a biphasic system) and the succedent liquid phase hydrogenolysis
4.2.2. Hydrodeoxygenation of biomass derivatives with HMF as an to DMF over CuRu/C catalyst has been shown to give high cata-
intermediate lytic eciency (up to 71% DMF yield; Table 8, Entry 1) [644].
Variation of reaction conditions and catalysts allows Combination of fructose-to-HMF dehydration over a solid acid
DMF, 2,5-bis(hydroxymethyl) tetrahydrofuran (BHMTF), 2,5- Amberlyst-15 catalyst and subsequent hydrogenolysis to DMF over
bis(hydroxymethyl)furan (BHMF), DMTHF, and ring-opened products RuSn/ZnO catalyst eciently produces DMF with an overall yield
like 5-hydroxy-2,5-hexanedione (HHD) to be selectively obtained of 92% with no leaching of the active sites as assessed with ICP-
from HMF hydrogenation, as shown in Fig. 37. DMF, which has AES analyses (Table 8, Entry 2) [645]. Starting from glucose,
a moderate boiling point (9294 C) and high energy den- Chidambaram and Bell [646] reported that HPAs such as 12-
sity (31.5 MJL1) is of high interest [639641]. Using different sugars molybdophosphoric acid (12-MPA) were extremely active for
as substrates, a series of catalytic systems ecient for the trans- dehydration of glucose in a mixed solution consisting of [EMIM][Cl]
formation of biomass derivatives into DMF with HMF or and acetonitrile, producing approximately 100% yield of HMF after
5-chloromethylfurfural (CMF) as an intermediate have been eluci- 3 h at 120 C (Table 8, Entry 3), while carbon-supported metals such
dated [642,643]. as Pd/C catalyst in a second step could convert 4447% HMF to DMF

Fig. 37. Major products in the hydrogenation/hydrogenolysis of HMF (5-hydroxymethylfurfural). DMF: 2,5-dimethylfuran, DMTHF: 2,5-dimethyltetrahydrofuran, BHMF: 2,5-
bis(hydroxymethyl)furan, HHD: 5-hydroxy-2,5-hexanedione.
Table 8
Hydrodeoxygenation of 5-hydroxymethylfurfural (Cat-2) derived from C6 sugars (Cat-1) to furanic compounds with summary of reaction conditions, H-donor, maximum catalytic activity and catalyst reusability.

Entry Substrate Catalyst Reaction conditionb H-donor Main product Catalytic activity Reusability Ref.
c
Cat-1 Cat-2 Solvent Temp. Time Conv. Yield Cycles Yield

1 Fructose (30 wt%) HCl 10 wt%a CuRu/C 1-BuOH 220 C 10 h 0.68 MPa H2 DMF 100% 71% NMd NM [644]
2 Fructose (17.6 wt%) Amberlyst-15 5 wt% RuSn/ZnO 1-BuOH 240 C 0.5 h1e 0.1 MPa H2 DMF 100% 92% 5 ~90% [645]
3 Glucose (9 wt%) 12-MPA 0.2 wt% Pd/C EMIMCl + MeCN 120 C 3h 6.2 MPa H2 DMF 100% ~100% NM NM [646]
4 Xylose/Glucose (20/50 wt%) Sn-Mont + NbOPO4 3.5 wt% Ru/Co3O4 H2O + THF 170 C 24 h 1.0 MPa H2 MF 99% 91% NM NM [647]
[DMF] [99%] [93%]
5 HMF (5.3 wt%) 28.5 wt% PtCo/Ac 1-BuOH 180 C 2h 1.0 MPa H2 DMF 100% 98% 3 72% [648]
6 HMF (4.3 wt%) 53.7% Cu/ZnO 1,4-Dioxane 220 C 5h 1.5 MPa H2 DMF 100% 92% 5 10% [649]

H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194


7 HMF (2.5 wt%) 10 wt% Ni/Co3O4 THF 180 C 24 h 1.0 MPa H2 DMF 99% 76% 6 ~80% [650]
8 HMF (0.63 wt%) 10 wt% PdAu/C + HCl THF 60 C 6h H2 balloon DMF 99% 96% NM NM [651]
9 HMF (1.0 wt%) 3.2 wt% Ru/Co3O4 THF 130 C 24 h 0.7 MPa H2 DMF 99% 93% 6 ~89% [652]
10 HMF (0.5 wt%) 2 wt% Ru/NaY THF 220 C 1h 1.5 MPa H2 DMF 100% 78% 6 ~78% [653]
11 HMF (3.3 wt%) 0.2 wt% Pd/CZnCl2 THF 150 C 8h 0.8 MPa H2 DMF 99% 85% 5 ~66% [654]
12 HMF (0.5 wt%) 0.56 wt% Ru/HT 2-PrOH 220 C 4h 1.0 MPa H2 DMF 100% 58% 6 ~55% [641]
13 HMF (2.1 wt%) 0.4 wt% Pt/rGO 1-BuOH 120 C 2h 3.0 MPa H2 DMF 100% 73% 5 NM [655]
14 HMF (1.1 wt%) 7 wt% NiW2C/AC THF 180 C 3h 4.0 MPa H2 DMF 100% 96% 4 ~85% [656]
15 Fructose (36 wt%) H2SO4 H2SO4 + 5 wt% Pd/C THF 70 C 15 h FA DMF 100% 51% NM NM [657]
16 Fructose (36 wt%) FA H2SO4 + 5 wt% Ru/C THF 75 C 45 minf FA DMF 100% 32% NM NM [658]
17 Cellulose (10 wt%) DMA/LiCl + IL + FA H2SO4 + 5 wt% Ru/C THF 75 C 45 minf FA DMF 100% 16% NM NM [658]
18 Agar (10 wt%) DMA/LiCl + IL + FA H2SO4 + Ru/C THF 75 C 45 minf FA DMF 100% 27% NM NM [658]
19 HMF (6.3 wt%) 10 wt% NiPd/SiO2 H2O 40 C 2h 8.0 MPa H2 BHMTF 99% 96% NM NM [659]
20 HMF (6.3 wt%) 10 wt% Ni/SiO2 H2O 40 C 2h 8.0 MPa H2 BHMTF ~5% 0 NM NM [659]
21 HMF (6.3 wt%) 10 wt% Pd/SiO2 H2O 40 C 2h 8.0 MPa H2 BHMTF ~57% ~5% NM NM [659]
22 HMF (5 wt%) 1 wt% Ru/CeOx 1-BuOH/H2O 130 C 12 h 2.7 MPa H2 BHMTF 100% 91% NM NM [660]
23 HMF (5.0 wt%) 1 wt% Ru/MgZrOx 1-BuOH/H2O 130 C 12 h 2.7 MPa H2 BHMTF 100% 88% NM NM [660]
24 HMF (5 wt%) 1 wt% Ru/C 1-BuOH/H2O 130 C 12 h 2.7 MPa H2 BHMTF 100% 56% NM NM [660]
25 HMF (5 wt%) 1 wt% Pd/C 1-BuOH/H2O 130 C 12 h 2.7 MPa H2 BHMTF 100% 25% NM NM [660]
26 HMF (5.0 wt%) 1 wt% Pt/C 1-BuOH/H2O 130 C 12 h 2.7 MPa H2 BHMTF 83% 11% NM NM [660]
27 Fructose (36 wt%) [BMIM]Cl 5 wt%Pd/C H2O 50 C 3h 6.0 MPa H2 BHMTF 99% 63% NM NM [661]
[BHMF] [3%]
28 Fructose (36.0 wt%) [BMIM]Cl 5 wt% Ru/C H2O 50 C 3h 6.0 MPa H2 BHMTF 99% 27% NM NM [661]
[BHMF] [39%]
29 Fructose (36.0 wt%) [BMIM]Cl 5 wt% Ir/C H2O 50 C 3h 6.0 MPa H2 BHMTF 93% 10% NM NM [661]
[BHMF] [49%]
30 Fructose (36 wt%) [BMIM]Cl 5 wt% Pt/C H2O 50 C 3h 6.0 MPa H2 BHMTF 89% 5% NM NM [661]
[BHMF] [40%]
31 Fructose (36 wt%) [BMIM]Cl 5 wt% Ni/C H2O 50 C 3h 6.0 MPa H2 BHMTF 66% 5% NM NM [661]
[BHMF] [35%]
32 Fructose (36 wt%) [BMIM]Cl 5 wt% Ir/TiO2 H2O 50 C 3h 6.0 MPa H2 BHMTF 99% 1% NM NM [661]
[BHMF] [71%]
33 Fructose (4.2 wt%) Amberlyst-15 Ru/SiO2TM Cyclohexane/H2O 130 C 4h 4.0 MPa H2 BHMTF ~60% 65% 5 20% [662]
34 HMF (1.3 wt%) 1 wt% Au/CeO2 H2O 140 C 4h 3.8 MPa H2 BHMF 7% NM NM [663]
35 HMF (1.3 wt%) 1 wt% Au/La2O3 H2O 140 C 4h 3.8 MPa H2 BHMF 15% NM NM [663]
36 HMF (1.3 wt%) 1 wt% Au/Al2O3 H2O 140 C 4h 3.8 MPa H2 BHMF 100% 66% NM NM [663]
(continued on next page)

149
150
Table 8 (continued)

Entry Substrate Catalyst Reaction conditionb H-donor Main product Catalytic activity Reusability Ref.
c
Cat-1 Cat-2 Solvent Temp. Time Conv. Yield Cycles Yield

37 HMF (1.3 wt%) 1 wt% Au/ZrO2 H2O 140 C 4h 3.8 MPa H2 BHMF 32% 0 NM NM [663]
38 HMF (1.3 wt%) 1 wt% Au/TiO2 H2O 140 C 4h 3.8 MPa H2 BHMF 85% 0 NM NM [663]
39 HMF (1.3 wt%) 1 wt% Au/Ta2O5 H2O 140 C 4h 3.8 MPa H2 BHMF 40% 6% NM NM [663]
40 HMF (1.3 wt%) 1 wt% Au/TiO2SiO2 H2O 140 C 4h 3.8 MPa H2 BHMF 23% 0 NM NM [663]

H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194


41 HMF (1.3 wt%) 1 wt% SO4-ZrO2 H2O 140 C 4h 3.8 MPa H2 BHMF 17% 0 NM NM [663]
42 HMF (1.3 wt%) 1 wt% Au/Al2O3 H2O 120 C 2h 6.5 MPa H2 BHMF 100% 96% NM NM [663]
43 HMF (25 wt%) 1 wt% Pt/MCM-41 35 C 2h 0.8 MPa H2 BHMF 40% 6% NM NM [664]
44 HMF (25 wt%) 1 wt% Pt/MCM-41 H2O 35 C 2h 0.8 MPa H2 BHMF 100% 99% 6 98% [664]
45 Fructose (6 wt%) HI 1 wt% RhCl3xH2O H2O 140 C 2.5 h 2.1 MPa H2 DMTHF 100% 81% 7 86% [665]
[10] [80%]
46 Glucose (6 wt%) HI 1 wt% RhCl3xH2O H2O 140 C 16 h 2.1 MPa H2 DMTHF 100% 70% NM NM [665]
47 Inulin (6 wt%) HI 1 wt% RhCl3xH2O H2O 140 C 16 h 2.1 MPa H2 DMTHF 96% 73% NM NM [665]
48 Sucrose (6 wt%) HI 1 wt% RhCl3xH2O H2O 140 C 16 h 2.1 MPa H2 DMTHF 96% 82% NM NM [665]
49 Cellulose (6 wt%) HI 1 wt% RhCl3xH2O H2O/chlorobenzene 140 C 16 h 2.1 MPa H2 DMTHF 90% 54% NM NM [665]
50 Glucose (10 wt%) 2 wt% Cu/Al-SBA H2O 175 C 30 minf FA MFFA 99% 29% NM NM [666]
[DMF] [40%]
51 Glucose (10 wt%) 2 wt% Cu/AlZnSBA H2O 175 C 30 minf FA MFFA 99% 24% NM NM [666]
[DMF] [49%]
52 HMF (2.5 wt%) 5 wt% Pd/C Dioxane 120 C 20 h Decarbonylation FfA 95% 90% NM NM [667]
53 HMF (2.5 wt%) 5 wt% Pd/C Dioxane 120 C 15 h 0.2 MPa H2 + FA DMF 95% 85% NM NM [667]
54 HMF (2.5 wt%) 5 wt% Pd/C Dioxane 120 C 15 h 0.2 MPa H2 + AA DMF 95% 42% NM NM [667]
55 HMF (2.5 wt%) 5 wt% Pd/C Dioxane 120 C 15 h 0.2 MPa H2 DMTHF 95% 43% NM NM [667]
[DMF] [26%]
56 Fructose (4.5 wt%) Amberlyst-15 13 wt% Pd/C DMSO 80 C 15 h 1 MPa H2 HHD 95% 50% NM NM [668]
57 Fructose (4.5 wt%) Amberlyst-15 13 wt% Pd/C DMSO 80 C 36 h 3.5 MPa H2 HHD 95% 27% NM NM [668]
58 HHD (25 wt%) AmberliteIR-120H 1 wt% Pd/C H2O 90 C 2h 2 MPa H2 DMTHF 99% 99% 5 98% [669]
59 Fructose (10 wt%) 3.8 wt% sulde Pt/C EtOH 175 C 2h 10.3 MPa H2 DMTHF 100% 50% NM NM [670]
60 Fructose (10 wt%) 3.8 wt% sulde Pt/C H2O 175 C 2h 10.3 MPa H2 DMTHF 100% 9% NM NM [670]
a Metal loading in the catalyst.
b
Reaction conditions used for hydrodeoxygenation.
c
Product yield in the last cycle.
d NM: not mentioned.
e Weight hourly space velocity.
f Irradiation at 300 W.

DMF: 2,5-dimethylfuran, 12-MPA: 12-molybdophosphoric acid, EMIMCl: 1-ethyl-3-methylimidazolium chloride, MeCN: acetonitrile, THF: tetrahydrofuran, Y: Y type zeolites, HT: hydrotalcite, rGO: reduced graphene oxide, AC:
active carbon, FA: formic acid, IL: [DMA]+[CH3SO3] (DMA: N,N-dimethylacetamide), DMF: 2,5-dimethylfuran, BHMTF: 2,5-bis(hydroxymethyl)tetrahydrofuran, [BMIM]Cl: 1-butyl-3-methylimidazolium chloride, BHMF: 2,5-
bis(hydroxymethyl)furan, DMTHF: 2,5-dimethyltetrahydrofuran, AA: acetic acid, MFFA: 5-methylfurfuryl alcohol, FfA: furfuryl alcohol, DMSO: dimethylsulfoxide, HHD: 5-hydroxy-2,5-hexanedione.
H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194 151

in 1 h. The high selectivity of HMF catalyzed by HPAs is attributed selectivity at >99% conversion, which might be related to the
to the stabilization of reaction intermediates including 1,2-enediol, relatively higher specic rate of Pd in HMF hydrogenation
isomerized 2,3-enediol, and the in-situ formed furylhydroxymethyl (Pd Ru > Ir > Pt > Ni). Instead of multi-step catalytic steps in a single
ketone, while the presence of acetonitrile as a cosolvent inhibits the pot, a combination of acid (Amberlyst-15) and hydrophobic Ru/
formation of humins in both dehydration and subsequent hydro- SiO2-TM in a water/cyclohexane biphasic system can be used to
genation processes. With a THF/H2ONaCl biphasic system in achieve one-step hydrogenation of fructose to produce BHMTH in
combination with a dehydration process over Sn-Mont or NbOPO4 a maximum selectivity of 65% (Table 8, Entry 33), although the se-
catalyst and a succedent hydrogenolysis over Ru/Co3O4 catalyst, DMF lectivity toward BHMTH seems to be strongly dependent on the
and MF could be produced in high yields (>90%) from glucose/ acid catalyst used [662]. The selectivity of BHMTH increases in
xylose mixed substrates (Table 8, Entry 4) [647]. The in-situ the order of HY-zeolite (15%) < SO 4 2 /ZrO 2 (~40%) < Nb 2 O 5 P
separation of the upper organic phase containing furfural and HMF (~58%) < Amberlyst-15 (65%) < H2SO4 (75%), which is proportional-
is an important step for obtaining enhanced yields of hydroge- ly to the Bronsted acidity. It appears that the strong acid sites are
nated products. prone to accelerate the dehydration of fructose to HMF, thus facili-
A DMF yield of 98% from HMF (100% conversion within 10 min) tating the subsequent hydrogenation process to yield BHMTH
over PtCo bimetallic nanoparticles (3.6 0.7 nm diameter) in 2 h can without rehydration to LA.
be obtained without involving the catalytic step of sugar dehydra-
tion (Table 8, Entry 5) [648]. The small particle sizes and the stable 4.2.2.3. 2,5-bis(Hydroxymethyl)furan (BHMF). BHMF, which is ob-
homogeneous alloying in the hollow carbon spheres probably con- tained from the catalytic hydrogenation of the aldehyde in HMF, is
tribute to the high activity of the catalyst and the remarkable DMF used in polymers, resin additives, and intermediates for drugs and
yield (Table 8, Entry 5). Well-dispersed metal sites, well-controlled crown ethers [674,675]. Metal oxides supported gold with 1 wt%
surface sites of solid supports, and optimized reaction conditions Au loading prepared by deposition impregnation are active in the
can also provide enhanced catalytic reaction systems (Table 8, Entries hydrogenation of HMF to BHMF [663]. Among the catalysts (Table 8,
614) [641,649656]. Entries 3441), relatively high activity and selectivity toward BHMF
Instead of using H2 as H-donor, Thananatthanachon and Rauchfuss over Au/Al2O3 is obtained. For comparison, Au/La2O3 and Au/CeO2
[657] demonstrated that formic acid acts as an acid catalyst for are also selective in the production of BHMF but low reactivity is
fructose-to-HMF dehydration and as a hydrogen source over a Pd/C observed (Table 8, Entries 35 and 36). Whereas, almost no BHMF
catalyst for HMF deoxygenation to produce DMF, resulting in a total is produced from HMF catalyzed by those metal particles sup-
reaction eciency of about 51% after diethyl ether extraction (Table 8, ported on acidic metal oxides including TiO2, ZrO2, Ta2O5, TiO2SiO2
Entry 15). The one-pot conversion of lignocellulosic and algal biomass (TS) and sulfated zirconia (SZ) (Table 8, Entries 3741). Under op-
with a multicomponent catalytic system comprising [DMA]+[CH3SO3], timized reaction conditions, HMF is rapidly converted into BHMF
Ru/C and formic acid affords DMF in a maximum yield of 32% with Au/Al2O3 catalyst with a yield of >96% (Table 8, Entry 42). The
(Table 8, Entries 1618) [658]. For a possible reaction route, catalyst prepared under H2 at 200 C had the smallest gold par-
5-(formyloxymethyl)furfural was shown by 1H and 13C NMR spectra ticles with sub-nanometer diameter of 0.88 0.30 nm, indicating
to be a key intermediate. the formation of a magic number Au13 cluster. In neutral aqueous
medium, Pt/MCM-41 catalyst is able to hydrogenate HMF into BHMF
4.2.2.2. 2,5-bis(Hydroxymethyl)tetrahydrofuran (BHMTF). In the man- with complete conversion and selectivity of 99% (Table 8, Entry 43)
ufacture of plastics, 1,6-hexanediol is used on a large scale and it is [664]. Particularly, the amount of water plays a signicant role in
derived from petroleum sources [671]. It is possible to produce 1,6- the conversion and selectivity of the reaction. It is speculated that
hexanediol beginning from a biomass derivative BHMTF (Fig. 37). hydrogen bonding occurs between water molecules and the hy-
However, that method requires high temperatures and high hydro- droxyl groups on the support surface, which can help the water
gen pressures and large amounts of noble metal catalysts to obtain molecules surrounding the catalyst surface to disperse the cata-
BHMTF in high yields [672,673]. A series of NiPd bimetallic par- lyst. Thus, better catalytic activity (100% HMF conversion and ~100%
ticles supported on silica with various Ni/Pd molar ratios suitable BHMF selectivity) can be achieved in an aqueous medium by using
for the reaction have been prepared using a co-impregnation a specic amount of water (Table 8, Entry 44). However, too much
technique [659]. The best catalytic performance in the total water results in decreased conversion (71%) and selectivity (<90%),
hydrogenation of HMF to BHMTF (up to 96% yield) is for sup- which is possibly due to the reduced collisions between the reac-
ported catalyst (NiPd/SiO2) with a Ni/Pd ratio of 7 that is more tant and catalyst caused by substrate dilution.
selective than Pd/SiO2 and more active than commercial Raney Ni
(Table 8, Entries 1921). Ruthenium supported on materials such 4.2.2.4. 2,5-Dimethyltetrahydrofuran (DMTHF). DMTHF, which has
as ceria, magnesia-zirconia and -alumina with high isoelectric points low miscibility with water, a moderate boiling point (90 C) and high
exhibits higher BHMTF yields of 8891% than platinum and palla- energy density (31 MJL1), is a promising transportation fuel can-
dium catalysts at the same catalyst weight percent of 1 wt% (Table 8, didate. In a single step procedure, a coupled catalyst RhCl3/HI is able
Entries 2226) [660]. The superior overall selectivity to BHMTF is to promote the formation of DMTHF from poly- and monosaccha-
dependent not only on the high rates of hydrogenation (Ru > Pd) rides including corn stover, cellulose, inulin, sucrose, glucose and
other than CC scission reactions promoted by Pt, but also on the fructose, and a maximum DMTHF yield of 86% can be obtained
suitable solution acidity (pH = ~ 5) provided by solid supports or re- (Table 8, Entries 4549) [665]. It was found that HI functions as both
action media. Starting from carbohydrates, Cai et al. [661] performed a dehydrating agent in the initial sugar-to-HMF conversion and a
the direct production of furan-based diols with yields of 3489% reducing agent for the subsequent transformation of HMF to
via one-pot tandem reactions so that the controllable production 5-methylfurfural (MFf) [676]. The regeneration of HI from I2 formed
of BHMF or BHMTF is realized by selecting the suitable support and in the reduction step is realized by rhodium-catalyzed hydrogena-
metal species in a two-step process (Table 8, Entries 2732). After tion, and moreover, the metal catalyst also acts on the hydrogenation
checking various supported 5 wt% metal particles including Pd/C, of C:O and C:C bonds (Fig. 38). Before full hydrogenation of HMF
Ru/C, Ir/C, Ir/TiO2, Pt/C and Ni/C, the catalyst Ir/TiO2 affords >99% HMF to DMF, the key intermediate 5-methylfurfuryl alcohol (MFFA) is
conversion with BHMF in 95% selectivity from fructose, in which formed with a high selectivity of 60% in a short time (230 min)
both Ir particles and the reductive support TiO2 favor C:O hydro- over Cu-based catalysts (Table 8, Entries 50 and 51), and it is rapidly
genation. Under identical conditions, Pd/C provides BHMTF with 84% converted to DMF after prolonged reaction time [666].
152 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

Fig. 38. Proposed mechanism for the conversion of fructose to DMTHF (2,5-dimethyltetrahydrofuran). HMF: 5-hydroxymethylfurfuralhydroxymethylfurfural, MFf: 5-methylfurfural,
MFFA: 5-methylfurfuryl alcohol, DMF: 2,5-dimethylfuran, HHD: 5-hydroxy-2,5-hexanedione, DHH: 2,5-dihydroxyhexane. Adapted with permission from Ref. 676, Copy-
right 2012 Wiley VCH.

From above discussion, it is clear that the reactivity of HMF in conversion of fructose and inulin to the dominant product HMF and
the presence of metal-containing catalysts is diverse. Mitra et al. minor HHD, while further increasing the pressure of hydrogen from
[667] stated especially for HMF that the product distribution/ 1.0 to 2.0 MPa allows an increase in the yield of HHD by consum-
selectivity is affected by the additives. As shown in Fig. 39, Pd/C ing HMF in a concomitant route (Table 8, Entry 57). The combined
catalyst is capable of selectively mediating three broad reactions use of Pd/C and Amberlyst-15 in a single reactor for the ecient
of HMF covering decarbonylation, hydrogenation, and hydrogenolysis. and direct transformation of fructose and inulin into HHD illus-
Without adding any additives but at high reaction temperature trates the cooperativity of these two catalytic systems. Zhou et al.
(120 C) in suitable solvents like dioxane, HMF can be decar- [669] demonstrated that 1 wt% Pt/C and a solid acid AmberliteIR-
bonylated to FfA in high yields reaching 90% in air (Table 8, Entry 120H have a cooperative effect on conversion of HHD to DMTHF with
52). The decarbonylation of HMF is suppressed in the presence of yields up to 99% being obtained (Table 8, Entry 58) through a key
formic acid, while DMF is formed as the exclusive product (85% yield) intermediate 2,5-dihydroxyhexane (DHH; Table 8, Entries 59 and
in dioxane (Table 8, Entry 53). Similar to formic acid (FA), acetic acid 60) [670] as illustrated in Fig. 38. The dual catalyst system exhib-
(AA) also displays favorable effects on the production of DMF (42% its constant activity and DMTHF selectivity for ve recovery and reuse
yield) from HMF (Table 8, Entry 54). In the absence of formic acid, cycles. Single bifunctionalized solid materials are likely to improve
DMF undergoes further hydrogenation to DMTHF, indicating that catalytic eciency [678,679], wherein metal particles and Lewis acid
the acid inhibits the hydrogenation of the furan-ring (Table 8, Entry sites can synergistically catalyze the course of hydrogenations.
55).
In another case, the combined use of Pd/C and Amberlyst-15 4.2.3. Hydrodeoxygenation of biomass derivatives with furfural as
allows the one-pot transformation of fructose and inulin into an intermediate
5-hydroxy-2,5-hexanedione (HHD) with a maximum yield of 77% Furfural, which is the major dehydration product of pentoses,
and 100% carbon balance in a solution of THF and 0.3 wt% DMSO is capable of providing hydrogenated products through reduction
at 80 C and 1.03.5 MPa H2 partial pressure after 1536 h (Table 8, (Fig. 40) [680,681]. As shown in Route a, hydrogenation of the C:O
Entry 56) [668], implying that a synergistic effect exists for the acid group in HMF gives FfA, and the furan ring can be further hydro-
and hydrogenating sites in the reaction system [677]. An increase genated to yield tetrahydrofurfuryl alcohol (THFA). Rather than
of the amount of Amberlyst-15 from 11 to 35 wt% along with the reducing the unsaturated bond, the hydrogenolysis of CO bond
addition of 0.3 wt% of DMSO into THF leads to the complete of FfA to MF and 2-methyltetrahydrofuran (MTHF) can take place

Fig. 39. Reaction pathways of HMF (5-hydroxymethylfurfural) catalyzed by Pd/C with and without additives. FfA: furfuryl alcohol, DMF: 2,5-dimethylfuran, DMTHF: 2,5-
dimethyltetrahydrofuran, DMF: 2,5-dimethylfuran.
H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194 153

Fig. 40. Catalytic pathways for the hydrogenation of furfural. THFA: tetrahydrofurfuryl alcohol, FfA: furfuryl alcohol, MTHF: 2-methyltetrahydrahydrofuran, MF: 2-methylfuran,
THF: tetrahydrofuran. Adapted with permission from Ref. 680, Copyright 2012 Elsevier.

(Fig. 40, Route b). Moreover, furfuryl ether formed via a condensa- hydrogenation reaction, which deserves to be further studied for
tion process (Fig. 40, Route c), as well as THF from the cascade producing biomass-derived products with high selectivity.
decarbonylation at high temperature [682] and succedent hydro- Some other supported catalysts have been developed for the syn-
genation of furfural with furan as the intermediate (Fig. 40, Route thesis of FfA from furfural. In comparison to NiB and NiMoB catalyst,
d) can also be realized. amorphous NiMoB/Al2O3 alloy catalysts prepared from reduction of
-Al2O3 supported NiCl26H2O and (NH4)6Mo7O244H2O by NaBH4 could
4.2.3.1. Furfuryl alcohol (FfA). FfA is a promising feedstock for the convert 99% furfural into FfA with a high yield of 91% in methanol
production of resins, rubbers, polymers and valuable chemicals like (Table 9, Entries 1214) [702]. The CuCa/SiO2 catalyst prepared by
THFA and EL, and can also be used as a non-reactive diluent and solgel technique is found to have a relatively higher dispersion of
solvent [683689]. Industrial methods to produce FfA from furfu- copper than that fabricated by impregnation [703]. Correspond-
ral are typically mediated by CuCr based catalysts under H2 pressure ingly, the former catalyst (CuCa/SiO2-SG) affords a higher and more
via gas phase and liquid phase reactions [690,691]. However, these constant activity (99% selectivity and 100% conversion) than CuCa/
catalytic processes have high toxicity and only moderate ecien- SiO2-IM in the synthesis of FfA from furfural (Table 9, Entries 15 and
cy, therefore, the pre-requisite but challenging task is to design active 16), which might be attributed to the presence of calcium acting
catalytic systems that avoid the negative effects of this reaction as a structural promoter that improves catalyst stability as well as
system. Avoiding Cr additives, copper-containing catalysts such as selectivity.
CuFe, PdCu/SiO2, CuMgO, CuNiMgAlO and Cu/C could also The distribution of products is a strong function of the em-
give rise to high activity in terms of furfural conversion (up to ployed metal catalyst (Fig. 41) [704]. Over Cu/SiO2 catalyst, FfA in
98%) and FfA selectivity (up to 98%; Table 9, Entries 13) high selectivity with only a small amount of MF is obtained, while
[692694,718720]. Likewise, Co- and Ni-based amorphous cata- furan from furfural decarbonylation occurs with Pd/SiO2, and THF
lysts are highly selective for furfural-to-FfA conversion (around 99%; would be generated by further hydrogenation (Table 9, Entries 17
Table 9, Entries 47) [695698,721]. Unfortunately, the stability of and 18). Ring opening products (ROP) such as butanal, butanol and
these heterogeneous catalysts is rarely reported [722,723]. The re- butane would be formed in signicant amounts if Ni/SiO2 catalyst
usability of Pt/C catalyst has been explored in the liquid-phase is used (Table 9, Entry 19) [704]. In agreement with these results,
hydrogenation of furfural to FfA and no adverse effect is detected a DFT study illustrated that thermodynamics favors the produc-
for azeotropic mixtures of water and 2-propanol (Table 9, Entry 8) tion of furan and CO, while the formation of MF requiring lower
[699]. Nevertheless, when the support is changed from carbon to activation energy occurs through the dehydration of FfA or a de-
oxides, undesirable reactions such as hydrogenolysis of the CO hydrogenation pathway involving a methoxy intermediate [724].
bond, decarbonylation, furan ring hydrogenation and opening occurs Apart from metal types, the nature of supports affects catalytic per-
that causes a decrease in the selectivity of FfA from 99% to 94% with formance. In this regards, Mironenko et al. [705] demonstrated that
Pt/TiO2SiO2 or to 34% with Pt/SiO2 (Table 9, Entries 9 and10) [700]. 1.5 wt% Pd/CB (carbon black) affords a high FfA selectivity of 99%
After modication by SnBu4, the selectivity of Pt-based monome- from furfural (Table 9, Entries 20 and 21). In contrast, 1.5 wt% Pd/
tallic catalyst reaches 98%, and an almost constant FfA selectivity CNT (carbon nanotubes) are not active for FfA production under mild
of 96% is observed over the bimetallic catalyst PtSn0.3 during the three conditions, while the reduction of both C:O group and furan ring
cycles of reaction (Table 9, Entry 11) [701]. The nature of the cat- to THFA occur at 90 C (Table 9, Entries 22 and 23). Selectivity toward
alyst support directly affects the stability and selectivity of metal FfA directly from xylose in a one-step process over a dual catalyst
particles, and the use of carbon as the solid support seems to be system composed of Pt/SiO2 and sulfated ZrO2 strongly depends on
the good candidate for selective production of FfA. Bimetallic cata- the solvent that can inhibit the product polymerization [706]. With
lysts are likely to enhance both stability and selectivity for the partial the help of H2O/2-propanol in a ratio of 1:3 (v/v), a selectivity as
154
Table 9
Hydrodeoxygenation of furfural (Cat-2) derived from C5 sugars (Cat-1) for producing furfuryl alcohol (FfA) with summary of reaction conditions, H-donor, maximum catalytic activity and catalyst reusability.

Entry Substrate Catalyst Reaction conditionb H-donor Main product Catalytic activity Reusability Ref.

Cat-1 Cat-2 Solvent Temp. Time Conv. Yield Cycles Yieldc

1 Furfural (42 wt%) 33 wt%a CuFe2O4 Octane 160 C 5h 9 MPa H2 FfA 91% 90% 5 ~80% [692]
2 Furfural () 16 wt% 180 C 0.05 h1d 0.1 MPa H2 FfA 98% 96% NMe NM [693]
Cu/MgO
3 Furfural (33 wt%) 12.5 wt% CuNi/MgAlO Ethanol 200 C 2h 1 MPa H2 FfA 93% 83% NM NM [694]
4 Furfural (10 wt%) 65 wt% CoMoB Ethanol 100 C 3h 1 MPa H2 FfA 100% 100% NM NM [695]
5 Furfural (25 wt%) 34 wt% NiFeB Ethanol 100 C 4h 1 MPa H2 FfA 100% 100% NM NM [696]
6 Furfural (25 wt%) 75 wt% NiFeB Ethanol 80 C 3h 1 MPa H2 FfA 100% 97% NM NM [697]
7 Furfural (25 wt%) 76 wt% CoB Ethanol 80 C 1.4 h1d 1 MPa H2 FfA 100% 100% NM NM [698]
8 Furfural (1.6 wt%) 5 wt% Pt/C 2-PrOH/H2O 150 C 1.5 h 2.1 MPa H2 FfA 58% 57% NM NM [699]
9 Furfural () 5 wt% Pt/TiO2SiO2 150 C 2 h1d 0.1 MPa H2 FfA 68% 64% NM NM [700]
10 Furfural () 5 wt% Pt/SiO2 150 C 2 h1d 0.1 MPa H2 FfA 68% 23% NM NM [700]

H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194


11 Furfural (4 wt%) 70 wt% PtSn0.3 2-PrOH 100 C 8h 0.1 MPa H2 FfA 100% 96% 3 77% [701]
12 Furfural (20 wt%) 5 wt% NiMoB/Al2O3 MeOH 80 C 3h 5 MPa H2 FfA 99% 91% NM NM [702]
13 Furfural (20 wt%) 5 wt% NiB MeOH 80 C 3h 5 MPa H2 FfA 17% 15% NM NM [702]
14 Furfural (20 wt%) 5 wt% NiMoB MeOH 80 C 3h 5 MPa H2 FfA 87% 85% NM NM [702]
15 Furfural () 20 wt% CuCa/SiO2SG 130 C 0.33 h1d 0.1 MPa H2 FfA 100% 99% 80 h 99% [703]
16 Furfural () 20 wt% CuCa/SiO2SG 130 C 0.33 h1d 0.1 MPa H2 FfA 100% 94% 15-25 h 66% [703]
17 Furfural () 10 wt% Cu/SiO2 230 C 0.5 h1d 0.1 MPa H2 FfA 69% 68% NM NM [704]
[MF] [1%]
18 Furfural () 1 wt% Pd/SiO2 230 C 0.5 h1d 0.1 MPa H2 FfA 69% 10% NM NM [704]
[Furan] [41%]
(THF) (14%)
19 Furfural () 5 wt% Ni/SiO2 230 C 0.5 h1d 0.1 MPa H2 FfA 72% 18% NM NM [704]
[Furan] [31%]
(ROP) (18%)
20 Furfural (8.6 wt%) 1.5 wt% Pd/CB H2O 50 C 0.5 h 0.5 MPa H2 FfA 29% 29% NM NM [705]
21 Furfural (8.6 wt%) 1.5 wt% Pd/CB H2O 90 C 2h 2 MPa H2 FfA 76% 62% NM NM [705]
22 Furfural (8.6 wt%) 1.5 wt% Pd/CNT H2O 50 C 0.5 h 0.5 MPa H2 FfA 0 0 NM NM [705]
23 Furfural (8.6 wt%) 1.5 wt% Pd/CNT H2O 90 C 2h 2 MPa H2 FfA 95% 49% NM NM [705]
24 Xylose () ZrO2SO4 1 wt% Pt/SiO2 2-PrOH/H2O 130 C 6h 3 MPa H2 FfA 65% 33% 3 16% [706]
25 Furfural () 10 wt% Ni/SiO2 NM 140 C 1h 0.1 MPa H2 THFA 100% 94% NM NM [707]
26 Furfural (3.5 wt%) 60 wt% NiSn/TiO2 2-PrOH 110 C 75 min 3 MPa H2 FfA 99% 99% 5 43% [708]
27 Furfural (3.5 wt%) RANEY Ni/AlOH 2-PrOH 130 C 75 min 3 MPa H2 THFA 99% 99% NM NM [708]
28 Xylose (3.3 wt%) Amberlyst-15 5 wt% Ru/C H2O 165 C 50 min 2.5 MPa H2 THFA 78% 1% NM NM [709]
[Xylitol] [69%]
29 Xylose (3.3 wt%) Amberlyst-15 5 wt% Ru/C BuOH/H2O 165 C 450 min 2.5 MPa H2 THFA 41% 6% NM NM [709]
[Xylitol] [23%]
30 Xylose (3.3 wt%) Amberlyst-15 5 wt% Ru/C MTHF/H2O 165 C 350 min 2.5 MPa H2 THFA 72% 15% NM NM [709]
[Xylitol] [13%]
31 Xylose (3.3 wt%) Amberlyst-15 5 wt% Ru/C Cyclohexane/H2O 165 C 350 min 2.5 MPa H2 THFA 67% 19% NM NM [709]
[Xylitol] [7%]
32 Furfural () 59 wt% CuZn 250 C 0.3 h1d 0.1 MPa H2 MF 100% 87% NM NM [710]
[Furan] [ < 1%]
33 Furfural () 43 wt% CuCr 250 C 0.3 h1d 0.1 MPa H2 MF 100% 36% NM NM [710]
[Furan] [25%]
34 FfA () 59 wt% CuZn 220 C 0.3 h1d 0.1 MPa H2 MF 98% 92% NM NM [710]
[Furan] [ < 1%]
35 FfA () 43 wt% CuCr 220 C 0.3 h1d 0.1 MPa H2 MF 97% 60% NM NM [710]
[Furan] [23%]
(continued on next page)
Table 9 (continued)

Entry Substrate Catalyst Reaction conditionb H-donor Main product Catalytic activity Reusability Ref.

Cat-1 Cat-2 Solvent Temp. Time Conv. Yield Cycles Yieldc

36 Furfural () 5 wt% Ni/SiO2 250 C 0.025 h1d 0.1 MPa H2 FfA 51% 7% NM NM [711]
[Furan] [23%]
(MF) (1%)
37 Furfural () 5 wt% NiFe/SiO2 250 C 0.025 h1d 0.1 MPa H2 FfA 28% 5% NM NM [711]
[Furan] [4%]
(MF) (5%)
38 Furfural () 5 wt% NiFe/SiO2 250 C 0.1 h1d 0.1 MPa H2 FfA 96% 10% NM NM [711]
[Furan] [12%]

H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194


(MF) (39%)
39 Furfural () Mo2C 150 C 0.2 h1d 0.1 MPa H2 MF 12% 67% NM NM [712]
[Furan] [1%]
40 Xylose (12 wt%) H-mordenite 30 wt% CuFe Toluene/H2O 260 C/ 3 min/48 h1d 5.5 MPa N2/ Furfural/MF 98%/99% 98%/98% 20 h 98% [713]
252 C 0.1 MPa H2
41 Furfural (1 wt%) 2.2 wt% Ru/C 2-BuOH 180 C 10 h 2-BuOH MF 100% 76% NM NM [714]
42 Furfural (1 wt%) 2.2 wt% Ru/C 2-BuOH 180 C 5h 2-BuOH MF 85% 62% NM NM [714]
43 Furfural (1 wt%) 2.2 wt% Ru/C 2-PeOH 180 C 5h 2-PeOH MF 92% 68% NM NM [714]
44 Furfural (1 wt%) 2.2 wt% Ru/C 2-PrOH 180 C 5h 2-PrOH MF 89% 43% NM NM [714]
45 Furfural (1 wt%) 2.2 wt% Ru/C 1-BuOH 180 C 5h 1-BuOH MF 68% 32% NM NM [714]
46 Furfural (1 wt%) 2.2 wt% Ru/C 1-PrOH 180 C 5h 1-PrOH MF 76% 32% NM NM [714]
47 Furfural (1 wt%) 2.2 wt% Ru/C EtOH 180 C 5h 1-PrOH MF 72% 20% NM NM [714]
48 Furfural (1 wt%) 2.2 wt% Ru/C 2-MBuOH 180 C 5h 2-MBuOH MF 16% <1% NM NM [714]
49 Furfural (1 wt%) 2.2 wt% Ru/C t-BuOH 180 C 5h t-BuOH MF 12% 0 NM NM [714]
50 MF () Pt nanoparticles 40 C 0.01 MPa H2 1-Pentanol 98% f NM NM [715]
[2-Pentanol] [1%] f
(MTHF) (<1%) f
51 MF () Pt nanoparticles 95 C 0.01 MPa H2 1-Pentanol 45% f NM NM [715]
[2-Pentanol] [45%] f
(MTHF) (9%) f
52 Furfural (5 wt%) 3 wt% Pd/C 2-PrOH 220 C 5h 3.5 MPa H2 THF 100% 20% NM NM [716]
[THFA] [32%]
(MTHF) (18%)
53 Furfural (5 wt%) 3 wt% Pd/CaCO3 2-PrOH 220 C 5h 3.5 MPa H2 THF 92% 0 NM NM [716]
[THFA] [45%]
(MTHF) (15%)
54 LA (4.8 wt%) 2 wt% PtMo/H H2O 130 C 24 h 5 MPa H2 MTHF 99% 86% 3 85% [717]
a Metal loading in the catalyst.
b
Reaction conditions used for hydrodeoxygenation.
c Product yield in the last cycle.
d Weight hourly space velocity.
e NM: not mentioned.
f
Product selectivity.
THF: tetrahydrofuran, FfA: furfuryl alcohol, MF: 2-methylfuran, ROP: ring opening products, CB: carbon black, CNT: carbon nanotubes, THFA: tetrahydrofurfuryl alcohol, 2-BuOH: 2-butanol, 2-PeOH: 2-pentanol, 2-PrOH: 2-propanol,
1-BuOH: 1-butanol, 1-PrOH: 1-propanol, EtOH: ethanol, 2-MBuOH: 2-methyl-2-butanol, t-BuOH: tert-butanol, MTHF: 2-methyltetrahydrofuran, LA: levulinic acid.

155
156 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

Fig. 41. Plausible reaction routes in furfural hydrogenation with copper, palladium and nickel catalysts. THFA: tetrahydrofurfuryl alcohol, FfA: furfuryl alcohol, MF: 2-methylfuran,
THF: tetrahydrofuran. Adapted with permission from Ref. 704, Copyright 2011 Springer.

high as 51% toward FfA can be achieved directly from xylose (65% synthesis of crysanthemate pesticides, perfume and medical inter-
conversion) in a single pot (Table 9, Entry 24). For the hydrogena- mediates [729731]. Using furfural or FfA as the substrate, both
tion step, alcoholic solvents show outstanding effects on kinetics commercial CuZn and self-made CuCr bimetallic catalysts exhibit
due to their good hydrogen solubility. With respect to carbohy- nearly complete conversion for MF production (up to 96% yield) at
drate dehydration, the use of biphasic media is superior for producing 200300 C with the activity of Zn-promoted catalyst being supe-
furfural, which is realized by transferring the formed furanic com- rior to Cr-mediated ones (Table 9, Entries 3235) [710]. The high
pound into the organic phase, thus avoiding its degradation and yield of MF over Zn-promoted catalyst results from a synergistic effect
condensation in the acidic aqueous solution. of the metal and the weak acid sites [732]. The inuence of mono-
and bimetallic catalysts (i.e., Ni/SiO2 and NiFe/SiO2) on the product
4.2.3.2. Tetrahydrofurfuryl alcohol (THFA). THFA, which is exten- distribution in the conversion of furfural has been examined (Table 9,
sively used in industry as a chemical intermediate, is manufactured Entries 3638) [711], where it is found that monometallic catalyst
from the hydrogenation of FfA and furfural in the presence of nickel facilitated the formation of FfA and furan through separate hydro-
palladium, rhodium and platinum catalysts [725727]. The gas- genation and decarbonylation, while the yield of MF greatly increases
phase direct hydrogenation of furfural to THFA is preferable to liquid- through suppressing the formation of furan probably caused by Fe
phase reactions in terms of productivity and the prevention of species in bimetallic catalyst (Fig. 42). In this catalytic process, the
leaching [728]. Over Ni/SiO2 catalysts with <4 nm nickel particle sizes C:O hydrogenation occurs at low temperatures (ca. 140 C) via either
were prepared from the reduction of supported nickel nitrate, the an alkoxide or ahydroxyalkyl intermediate [733], while the CO
gas-phase total hydrogenation of furfural proceeds giving THFA at hydrogenolysis requires relatively high temperatures.
yields of 94% (Table 9, Entry 25) [707]. Moreover, both bulk and sup- Under ambient pressure at 150 C, molybdenum carbide (Mo2C)
ported SnNi-based alloy catalysts are active for converting furfural catalysts are robust for the cleavage of the C:O bond of furfural in
to THFA (up to 99% selectivity), and relatively high temperatures vapor phase HDO without concurrent scission of the side CC bond,
(ca. 130 versus 110 C) are necessary for ecient hydrogenation of yielding MF with a selectivity of ~5060% for less than 1% furan se-
C:O rather than C:C (Table 9, Entries 26 and 27) [708]. With the as- lectivity (Table 9, Entry 39) [712]. The metal-like sites on Mo2C
sistance of a biphasic system, Ordomsky et al. [709] combined the catalysts prove to be involved in the HDO of furfural via the invari-
processes of xylose dehydration with Amberlyst-15 and consecu- ance of MF site time yield normalized by the catalytic sites. A
tive furfural hydrogenation over a hydrophobic Ru/C catalyst into sequential reaction process of xylose-to-MF carried out with a con-
a single reactor. For increasing the hydrophobicity of solvents in the tinuous two-liquid-phase (aqueous-toluene) plug-ow reactor, in
order: 1-butanol < MTHF < cyclohexane, the hydrogenation of xylose which xylose was dehydrated to furfural (98% yield) in water over
to xylitol is suppressed, thus facilitating the formation of THFA (up H-mordenite at 260 C and 5.5 MPa N2 and furfural extracted from
to 50% selectivity) directly from xylose via the intermediate furfu- the aqueous phase into the toluene was further hydrogenated to
ral (Table 9, Entries 2831). give MF (98% yield) at 252 C and 0.1 MPa H2 (gas ow: 48 h1) over
a CuFe catalyst (Table 9, Entry 40) [713]. Besides H2, alcohol hy-
4.2.3.3. 2-Methylfuran (MF). Analogous to DMF, 2-methylfuran is a drogen donor was found to be ecient for MF production (up to
model biomass-derived liquid fuel that can be used for the 76% yield) from the catalytic transfer hydrogenation of furfural over
H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194 157

Fig. 42. Reaction pathways for furfural conversion over Ni-based catalysts. FfA: furfuryl alcohol, MF: 2-methylfuran. Adapted with permission from Ref. 711, Copyright
2011 Elsevier.

a calcined Ru/C catalyst in liquid phase at 110200 C [714]. The as an effective support for high dispersion of Pt nanoparticles and
yield of MF is inuenced by the alcohol dehydrogenation activity MoOx, as well as acid catalyst promoting the cyclodehydration of
as well as solvent polarity, and increased following the order: 1,4-pentanediol to MTHF.
2-methyl-2-butanol < tert-butanol < ethanol < 1-propanol 1-
butanol < 2-propanol < 2-butanol 2-pentanol (Table 9, Entries 4.2.4. (Hydrolysis)hydrogenationcyclization of biomass
4149). derivatives to -valerolactone (GVL)
The chemical, GVL, is useful as a solvent [740742], intermedi-
4.2.3.4. 2-Methyltetrahydrofuran (MTHF). The chemical, MTHF, which ate [743745], perfume and food additive [746], and in particular,
can be used as a pharmaceutical solvent and an oxygenated gaso- is a potential fuel additive [747,748]. One possible pathway to syn-
line additive in P-series fuel [734738] can be synthesized from thesize GVL from biomass-derived LA involves an unstable
selective hydrogenation of MF over cubic platinum nanoparticles intermediate -hydroxyvaleric acid produced via hydrogenation, fol-
of 7 nm average size (Fig. 43), where the distribution of products lowed by elimination of a water molecule in the intramolecular
varies with reaction temperature (40120 C) [715]. At 40 C, the esterication to give GVL through ring closure (Fig. 44) [749,750].
main product is 1-pentanol (~98% selectivity) formed via a ring- In another pathway, angelica lactone ( and isomer) formed from
opening process; while the dominant ring-opening product changes LA dehydration is hydrogenated to produce GVL [751,752]. To achieve
to 2-pentanol with an increase of temperature to 95 C (Table 9, high performance in the synthesis of GVL from different feed-
Entries 50 and 51). Unfortunately, the relative concentration of the stocks, much attention has been paid to develop environmentally
hydrogenated ring product MTHF remains low, regardless of how benign and cost ecient processes with heterogeneous catalysis.
temperature is varied. To solve the mass transfer limitations caused Compared with in-situ hydrogen sources, the catalytic transfer hy-
by low solubility of hydrogen gas in the solvent, Liu et al. [739] in- drogenation (CTH) of levulinates via MeerweinPonndorfVerley
troduced a packed-bed microreactor with Pd/C catalyst offering a (MPV) reduction with alcohols is thought to be a favorable method
safe and alternative approach to high-pressure hydrogenation of MF for GVL production. Handling liquid alcohols used in the CTH route
into MTHF. In another case, the decarbonylation of furfural to furan is not only more convenient than molecular H2 but also allows high
over the same Pd/C catalyst was demonstrated to be a prerequi- selectivity of the hydrogenation of alkyl levulinates to GVL without
site for THF formation (Table 9, Entries 52 and 53) [716]. In the over-hydrogenating GVL to byproducts. Furthermore, the CTH route
presence of a metalacid bifunctional catalyst 2 wt% PtMo/H, to GVL can be carried out over inexpensive base metal catalysts with
Mizugaki et al. [717] demonstrated that levulinic acid (LA) could Zr, Ni and Sn as the active sites, which is attractive for the produc-
be successively hydrogenated to 1,4-pentanediol and dehydrated to tion of GVL on a commercial scale.
form MTHF in a yield of 86% (Table 9, Entry 54). A synergistic effect
between Pt nanoparticles and MoOx species promotes the hydro- 4.2.4.1. Direct catalytic hydrogenation. In general, LA and esters can
genation of LA to 1,4-pentanediol, while H possesses a dual function be produced from C6 sugars via an anaerobic oxidation process

Fig. 43. Related products formed in 2-methylfuran (MF) hydrogenation over platinum nanoparticles. MTHF: 2-methyltetrahydrahydrofuran. Adapted with permission from
Ref. 715, Copyright 2011 American Chemical Society.
158 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

Fig. 44. Reaction pathways to produce GVL (-valerolactone) from LA (levulinic acid).

[753757]. If furfural synthesized from C5 carbohydrates is in-situ (Table 10, Entries 58) [766,767]. The complete LA conversion is ob-
hydrogenated into FfA, then high yields of LA are obtained in a single tained at 130 C in an alcohol solvent (e.g., ethanol) over ruthenium
pot as well via subsequent rehydration [758,759]. Zeolites, which supported with different solid acid supports such as TiO2, SiO2 and
are acid catalysts active for hydrolysis [760], are ecient for the syn- Al 2 O 3 (Table 10, Entries 912) [768]. Cross-linked sulfonated
thesis of LA from xylose under hot-compressed water [761]. In a polyethersulfone supported Ru nanoparticle catalysts highly hy-
one-pot process, a maximum LA yield of 30% is achieved over 0.25 M drogenate LA (88% conversion) into GVL (100% selectivity) at 70 C
NaOH-treated HY zeolite at 170 C and 1.5 MPa N2 partial pressure (Table 10, Entries 1317) [769]. The combined use of a ruthenium
in 3 h, and the in-situ generated formic acid is thought to be the catalyst (Ru/C) with an acid such as Amberlyst-70 or Amberlyst-
hydrogen source in the key step of furfural-to-FfA hydrogenation. 15, niobium phosphate, and oxides increases the reaction rate in
Starting from biomass derived LA, a number of studies focus on using both esterication and hydrogenation steps, and a high GVL yields
metal particles and oxides as catalysts to produce GVL under mo- of 99% with an activity of 558 h1 are realized from LA over a co-
lecular hydrogen, formic acid, and alcohols. When different solvents catalyst consisting of Ru/C and Amberlyst-70 (Table 10, Entries 18
like water and alcohols are employed, reaction pathways from and 19) [770]. Many other types of metal particles have been studied
LA to GVL are dissimilar (Fig. 45) [762]. In water medium, the for this catalytic process, namely iridium nanoparticles and com-
rst step is direct hydrogenation of the keto group in LA to give plexes (Table 10, Entries 2022) [771773], palladium based mono
4-hydroxyvaleric acid, followed by dehydration to yield cyclic GVL, and bimetallic catalysts (Table 10, Entries 2325) [774776], Raney
while GVL in the presence of methanol is formed through sequen- and supported Ni catalysts (Table 10, Entries 2628) [777779], and
tial esterication of the carboxyl group to methyl levulinate (ML), noble-metal-free catalysts such as copper (Table 10, Entries 29
hydrogenation to methyl 4-hydroxypentanoate, and intramolecu- 31) [780782], ferrous (Table 10, Entry 32) [783] and cobalt (Table 10,
lar transesterication to eliminate methanol. Entry 33) [784] nanoparticles, which are ecient to synthesize GVL
Ruthenium-based catalysts often exhibit high activity in the from LA under a H2 atmosphere. Nevertheless, relative high hydro-
process of LA-to-GVL conversion, and due attention has been paid gen pressures and reaction temperatures are always required.
to seek mild reaction conditions [763]. In a continuous down-ow Instead of using LA as the starting material, the direct synthe-
xed-bed reactor system, 5% Ru/C in comparison to Pt/C and Pd/C sis of GVL from C5- and C6-sugar sources is possible without isolating
is found to be more active (100% conversion) and product selec- the intermediate LA from the reaction mixture, which may reduce
tive toward GVL (up to 100% selectivity) in dioxane from the vapor the number of processing steps (Fig. 46). Using molecular hydro-
phase hydrogenation of LA (Table 10, Entries 13) [764], and com- gen as hydrogen donor, an acid catalyst (e.g., triuoroacetic acid)
parable GVL selectivity (99%) and LA conversion (92%) are obtained in combination with a hydrogenation catalyst Ru/C could produce
in methanol over the same catalyst Ru/C at a lower temperature of GVL in yields of 2962% from glucose, fructose, sucrose and cellu-
130 C (Table 10, Entry 4) [765]. When an acidic support (e.g., lose via a two-step process conducted (Table 10, Entries 3437) [785].
hydroxyapatite and DOWEX 50WX2-100) is used, reaction tem- It is clear that a strong acid is required to produce LA from C6-
peratures tend to decrease for the one-pot conversion of LA to GVL sugars in the rst step, and then integration with the hydrogenation

Fig. 45. Catalytic hydrogenation of levulinic acid (LA) in water or methyl levulinate (ML) in methanol to form -valerolactone (GVL).
Table 10
Catalytic conversion of carbohydrates or levulinic acid/levulinates derived from carbohydrates for producing -valerolactone with summary of reaction conditions, H-donor, maximum catalytic activity and catalyst reusability.

Entry Substrate Catalyst a Reaction condition b H-donor Main Catalytic activity Reusability Ref.
product
Solvent Temp. Time Conv. Yield Cycles Yieldc

1 LA (10.0 wt%) 5 wt% Ru/C 1, 4-Dioxane 265 C 0.512 h1 d 0.1 MPa H2 GVL 100% 99% 7d 97% [764]
[Anjelica [1%]
lactone]
2 LA (10.0 wt%) 5 wt% Pd/C 1, 4-Dioxane 265 C 0.512 h1d 0.1 MPa H2 GVL 100% 90% NM e NM [764]
[Anjelica [10%]
lactone]
3 LA (10.0 wt%) 5 wt% Pt/C 1, 4-Dioxane 265 C 0.512 h1d 0.1 MPa H2 GVL 100% 30% NM NM [764]
[Anjelica [69%]
lactone]

H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194


4 LA (5.0 wt%) 5 wt% Ru/C MeOH 130 C 160 min 1.2 MPa H2 GVL 92% 91% 4 20% [765]
5 LA (5.0 wt%) 5 wt% Ru/hydroxyapatite H2O 70 C 4h 0.5 MPa H2 GVL 99% 99% 5 89% [766]
6 LA (5.0 wt%) 5 wt% Pd/hydroxyapatite H2O 70 C 4h 0.5 MPa H2 GVL 26% 23% NM NM [766]
7 LA (5.0 wt%) 5 wt% Pt/hydroxyapatite H2O 70 C 4h 0.5 MPa H2 GVL 42% 37% NM NM [766]
8 LA (0.3 wt%) 0.87 wt% Ru/DOWEX 50WX2-100 H2O 70 C 0.15 min1d 0.5 MPa H2 GVL 100% 99% 33 h 90% [767]
9 LA (5.0 wt%) 5 wt% Ru/C EtOH 130 C 160 min 1.2 MPa H2 GVL 76% 61% NM NM [768]
10 LA (5.0 wt%) 5 wt% Ru/TiO2 EtOH 130 C 160 min 1.2 MPa H2 GVL 67% 62% NM NM [768]
11 LA (5.0 wt%) 5 wt% Ru/Al2O3 EtOH 130 C 160 min 1.2 MPa H2 GVL 38% 32% NM NM [768]
12 LA (5.0 wt%) 5 wt% Ru/SiO2 EtOH 130 C 160 min 1.2 MPa H2 GVL 83% 77% NM NM [768]
13 LA (5.0 wt%) 2 wt% Ru/SPES H2O 70 C 2h 3.0 MPa H2 GVL 88% 88% 5 90% [769]
14 LA (5.0 wt%) 2 wt% Ru/SiO2 H2O 70 C 2h 3.0 MPa H2 GVL 22% 21% NM NM [769]
15 LA (5.0 wt%) 2 wt% Ru/C H2O 70 C 2h 3.0 MPa H2 GVL 55% 53% NM NM [769]
16 LA (5.0 wt%) 2 wt% Ru/SiO2 + 2 wt% Amberlyst-15 H2O 70 C 2h 3.0 MPa H2 GVL 40% 39% NM NM [769]
17 LA (5.0 wt%) 2 wt% Ru/C + 2 wt% Amberlyst-15 H2O 70 C 2h 3.0 MPa H2 GVL 68% 67% NM NM [769]
18 LA (5.0 wt%) 5 wt% Ru/C + 12 wt% Amberlyst-15 H2O 70 C 518.3 h1d (3 h) 3.0 MPa H2 GVL 91% 90% NM NM [770]
19 LA (5.0 wt%) 5 wt% Ru/C + 12 wt% Amberlyst-70 H2O 70 C 569.6 h1d (3 h) 3.0 MPa H2 GVL 100% 100% 5 95% [770]
20 LA (5.0 wt%) 4.5 wt% Ir/CNT H2O 50 C 1h 2.0 MPa H2 GVL 96% 95% NM NM [771]
21 LA (15.0 wt%) 0.01 mol% iridium complex Acidic H2O 120 C 4h 1.01 MPa H2 GVL 100% 98% 5 94% [772]
22 LA (10.0 wt%) 0.05 mol% [Ir(COE)2Cl]2 EtOH + 47wt% KOH 100 C 15 h 5.0 MPa H2 GVL 100% 96% NM NM [773]
23 LA (2.5 wt%) 2 wt% Pd-2 wt% Au/HMS H2O 160 C 1h 15.0 MPa H2 GVL 100% 99% 3 65% [774]
24 LA (37.7 wt%) 5 wt% Pd/CNT H2O 200 C 6h 6.0 MPa H2 GVL 58% 56% NM NM [775]
25 LA (50.0 wt%) 5 wt% Pd/SiO2 H2O 180 C 6h 9.0 MPa H2 GVL 97% 97% 4 ~90% [776]
26 LA (6.9 wt%) 10 wt% Ni7 wt% MoOx/C H2O 140 C 5h 0.8 MPa H2 GVL 100% 97% NM NM [777]
27 LA (1 mL/h) 30 wt% Ni/SiO2 H2O 250 C 0.8506 h1d 0.1 MPa H2 GVL 99% 87% 25 h 85% [778]
28 LA (2.5 wt%) 40 wt% Raney Ni 2-PrOH 100 C 4h 1.5 MPa H2 GVL 100% 100% 5 55% [779]
29 LA (10.0 wt%) 5 wt% Cu/Al2O3 H2O 265 C 0.169 h1d H2 stream GVL 98% 85% 25 h 70% [780]
30 LA (16.9 wt%) 10 wt% CuCr H2O 200 C 10 h 7.0 MPa H2 GVL 100% 91% NM NM [781]
31 LA (10.0 wt%) 5 wt% Cu/ZrO2 H2O 265 C 0.169 h1d H2 stream GVL 81% 67% 28 h 60% [782]
32 LA (10.0 wt%) 4 wt% Fe/C nanoparticles H2O 170 C 3h 0.5 MPa H2 GVL 100% 99% 6 95% [783]
33 LA (5.0 wt%) 5 wt% Co2O3 H2O 130 C 13 h 3.0 MPa H2 GVL 100% 98% 10 50% [784]
(3 h)
34 Fructose (16.5 wt%) 11.4 wt% TFA + 5 wt% Ru/C H2O 180 C 8h 6.0 MPa H2 GVL 62% NM NM [785]
35 Glucose (16.5 wt%) 11.4 wt% TFA + 5 wt% Ru/C H2O 180 C 8h 6.0 MPa H2 GVL 38% NM NM [785]
36 Sucrose (16.5 wt%) 11.4 wt% TFA + 5 wt% Ru/C H2O 180 C 8h 6.0 MPa H2 GVL 52% NM NM [785]
37 Cellulose (16.5 wt%) 11.4 wt% TFA + 5 wt% Ru/C H2O 180 C 8h 6.0 MPa H2 GVL 29% NM NM [785]
38 Cellulose (5.0 wt%) 80 wt% AlNbOPO4 + 5 wt% Ru/C H2O 180 C 24 h + 12 h 5.0 MPa H2 GVL 53% NM NM [786]
39 Cellulose (36 mM) 0.5 M H2SO4 + Raney Ni MTHF 220 C/125 C 8 h/0.5 mL min1d H2 stream LA/GVL 100% 50%/50% NM NM [787]
(continued on next page)

159
160
Table 10 (continued)

Entry Substrate Catalyst a Reaction condition b H-donor Main Catalytic activity Reusability Ref.
product
Solvent Temp. Time Conv. Yield Cycles Yieldc

40 Giant reed (7.0 wt%) 0.4 M HCl/5 wt% Ru/C + NbOPO4 H2O 200 C/70 C 1 h/5 h 3.0 MPa H2 LA/GVL 100% 61%/17% 3 15% [788]
41 FfA (5 wt%) 60 wt% [BMIm-SH][HSO4]/5 wt% Ru/C MeOH 130 C 2 h/5 h 3.4 MPa H2 LA/GVL 99% 94%/89% 4 75% [789]
42 LA (1 wt%) 200 wt% ZrO2 2-BuOH 150 C 16 h 2-BuOH GVL 100% 92% NM NM [790]

H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194


43 LA (1 wt%) 200 wt% MgO/ZrO2 2-BuOH 150 C 16 h 2-BuOH GVL 100% 54% NM NM [790]
44 LA (1 wt%) 200 wt% -Al2O3 2-BuOH 150 C 16 h 2-BuOH GVL 80% 56% NM NM [790]
45 LA (1 wt%) 200 wt% CeZrOx 2-BuOH 150 C 16 h 2-BuOH GVL 43% 11% NM NM [790]
46 EL (5 wt%) 50 wt% ZrO(OH)2xH2O 2-PrOH 200 C 1h 2-PrOH GVL 94% 88% 10 50% [791]
47 EL (5 wt%) 50 wt% ZrO2 EtOH 250 C 3h EtOH GVL 96% 82% 4 43% [792]
48 EL (2.4 wt%) 138.9 wt% ZrHBA 2-PrOH 150 C 4h 2-PrOH GVL 100% 94% 5 92% [793]
49 EL (2.4 wt%) 173.9 wt% Zr-Beta 2-Pentanol 150 C 4h 2-Pentanol GVL 100% 96% 87 h 99% [794]
50 LA (7.0 wt%) 5 wt% Raney Ni 2-PrOH 25 C/120 C 9 h/1 h 2-PrOH GVL 100% 99%/94% NM NM [795,796]
51 LA (6.0 wt%) 5 wt% Pd/C + 2 equiv. KOH EtOH 50 s f EtOH GVL 86% 5 82% [797]
52 LA (47.9 wt%) 0.1 mol% RuP/SiO2 + 1 equiv. NaOH H2O 150 C 12 h 1 equiv. formic acid GVL 100% 96% NM NM [798]
53 LA (47.9 wt%) 0.1 mol% RuP/SiO2 H2O 150 C 1h 1 equiv. formic acid GVL 447 h1 NM NM [798]
(TOF)
54 LA (47.9 wt%) 0.1 mol% RuS/SiO2 H2O 150 C 1h 1 equiv. formic acid GVL 173 h1 NM NM [798]
(TOF)
55 LA (47.9 wt%) 0.1 mol% RuN/SiO2 H2O 150 C 1h 1 equiv. formic acid GVL 112 h1 NM NM [798]
(TOF)
56 LA (71.9 wt%) 0.04 mol% Shvo catalyst Formic acid 100 C 8h 1.5 equiv. formic acid GVL 100% 100% NM NM [799]
57 LA (20.0 wt%) 0.3 wt% [Ru3(CO)12] + 18.3 mol% Et3N H2O 130 C 24 h 2 equiv. formic acid GVL 100% 100% 3 99% [800]
58 LA (5.0 wt%) 0.1 mol% Au/ZrO2 H2O 150 C 6h 1 equiv. formic acid GVL 100% 99% NM NM [801]
59 BL (10.0 mol%) 0.1 mol% Au/ZrO2 H2O 170 C 6h 1 equiv. formic acid GVL 98% 95% NM NM [802]
60 LA (5.0 wt%) 0.1 mol% Cu/ZrO2 H2O 200 C 5h 1 equiv. formic acid GVL 100% 100% NM NM [803]
a
Metal loading in the catalyst or the catalyst dosage relative to the substrate.
b
Reaction conditions used for hydrodeoxygenation.
c Product yield in the last cycle.
d Weight hourly space velocity.
e NM: not mentioned.
f
Microwave irradiation.
LA: levulinic acid, MeOH: methanol, GVL: -valerolactone, DOWEX 50WX2-100: a SO3H-functionalized gel-type resin, EtOH: ethanol, SPES: cross-linked sulfonated polyethersulfone, CNT: carbon nanotubes, HMS: mesoporous
silica, TFA: triuoroacetic acid, MTHF: 2-methyltetrahydrofuran, FfA: furfuryl alcohol, EL: ethyl levulinate, ZrHBA is prepared by the coprecipitation of 4-hydroxybenzoic acid dipotassium salt and ZrOCl2, TOF: turnover fre-
quency, BL: butyl levulinate, Et3N: triethylamine.
H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194 161

Fig. 46. Production of -valerolactone (GVL) from C5- and C6-sugars involving levulinic acid (LA), furfuryl alcohol (FfA), 5-hydroxymethylfurfural (HMF), and furfural as
intermediates.

step over a metal catalyst yields GVL (Table 10, Entries 38 and 39) [790]. Among the catalytic systems, zirconia-based catalysts are fre-
[786,787,804,805]. Employing GVL as a co-solvent, transformation quently studied. Chia et al. [790] found that metal oxides such as
of C6-sugars, in particular, cellulose in a biphasic reaction system ZrO2, MgO/ZrO2, -Al2O3, and CeZrOx could eciently catalyze the
consisting of GVL and aqueous solution could eliminate the need transfer hydrogenation of LA and esters with 2-butanol as solvent
to purify GVL from the extraction solvent [806808]. By adopting and hydrogen donor, giving GVL in a maximum yield of 92% (Table 10,
a bifunctional catalytic system based on Ru/C and niobium oxide Entries 4245). Basic sites in a cooperative manner with acid sites
or niobium phosphate, straight production of GVL from water slur- of ZrO2-based catalysts are proposed to be active for the MPV re-
ries of giant reed was realized, producing a moderate GVL yield of action, leading to concerted direct CTH through a six-membered
17% with an almost complete conversion of intermediate LA cyclic transition state. Similarly, ZrO(OH)2xH2O is active for the con-
(Table 10, Entry 40) [788]. The acid component favors initial acti- version of EL (94% conversion) to GVL with a selectivity of 95% when
vation of the carbonyl group toward hydrogenation and subsequent 2-propanol is used as hydrogen donor (Table 10, Entry 46) [791].
esterication reaction to produce GVL. In the case of C5-sugar de- The selectivities to GVL and by-products are not affected notice-
rivatives, a combination of an acidic IL [BMImSH][HSO4] and 5% ably by reaction temperature, duration and catalyst loading. Although
Ru/C catalyst is ecient for the sequential alcoholysis and hydro- hydrogen transfer from ethanol to EL is likely to be suppressed when
genation of FfA to GVL via the corresponding levulinic esters in temperatures exceed 240 C, a high GVL yield of 82% with 96% EL
methanol, ethanol, n-butanol and isopropyl alcohol solvents conversion is obtained in supercritical ethanol at 250 C after 3 h
(Table 10, Entry 41) [789], while an extra hydrogenation step to over an amorphous ZrO2 catalyst calcined at 300 C with a high spe-
produce FfA is necessary when furfural used as substrate [809]. Since cic surface area and a large number of acidbase sites (Table 10,
LA is the shared intermediate for the production of GVL from both Entry 47) [792]. After recycling of ZrO2 for 4 times, EL conversion
C5- and C6-sugars, the integrated conversion of hemicellulose and and the GVL yield gradually decline to 55 and 43%, respectively. The
cellulose to GVL has also been proposed [810]. This process allows deposition of humins, probably generated by an aldol condensa-
for the simultaneous conversion of hemicellulose and cellulose to tion among EL, GVL and aldehyde, onto the surface of ZrO2 are
small molecules in a single reactor, thus eliminating pre-treatment speculated to cause the partial deactivation of ZrO2. A porous Zr-
steps that would be required to fractionate biomass. The inte- containing catalyst as well as zirconiumBeta zeolite also prove to
grated process has great potential for directly converting sugar be robust for the transformation of EL and LA to GVL via MPV re-
components into a common product LA with improved selectivity duction (Table 10, Entries 48 and 49) [793,794], and the isolated
so that it also offers the possibility of producing downstream chemi- Lewis acid and base sites contribute to the high catalytic activity
cals like GVL. [811]. The stability of zirconium enhanced by organic or inorganic
framework renders the catalysts to be reusable without notice-
4.2.4.2. Catalytic transfer hydrogenation (CTH). As an attractive al- able decreases in the conversion, yield and selectivity after several
ternative to the hydrogenation of LA to GVL using molecular H2 over consecutive cycles. Furthermore, some other metals like Raney Ni
metal catalyst, CTH with the hydrogen source being a secondary (Table 10, Entry 50) [795,796] and Pd/C (Table 10, Entry 51) [797]
alcohol through the MPV reaction has been proposed as in Fig. 47 are stable and effective for the hydrogenation of LA and EL to GVL

Fig. 47. Catalytic transfer hydrogenation (CTH) of levulinic acid (LA) and its esters to -valerolactone (GVL) in a secondary alcohol.
162 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

Fig. 48. Catalytic hydrogenation of LA (levulinic acid) to GVL (-valerolactone) using formic acid or H2 as hydrogen source.

in a secondary alcohol solvent such as 2-sec-butyl-phenol and iso- H2 rather than CO and H2O. The use of inexpensive and abundant
propanol. The hydride shift is conrmed to be the rate-limiting step, alcohols as hydrogen donor and solvent over cheap acidbase bi-
and increasing polarity of the hydrogen donor leads to a decrease functional solid catalysts appears to be promising for GVL production
in the reaction rates. Importantly, a rst-order dependence on alkyl through MPV reduction. In this regard, the development of
levulinate and secondary alcohol supports a dual-binding mecha- functionalized catalysts active for CTH process is of high demand.
nism, where the ketone and alcohol interact with a single metal site
to form a six-membered transition state [811]. A synergic effect 4.2.4.3. Upgrading of GVL. GVL is a platform molecule that has many
between base and acid sites has been demonstrated to be respon- potential applications in the production of chemicals and fuels
sible for the enhanced activity in levulinates-to-GVL conversion (Fig. 49) [819]. Through hydrogenation, 1,4-pentanediol can be
[812814], wherein basic sites (e.g., O2) assisted with Lewis acidic formed, which may readily undergo dehydration to give MTHF. Sub-
sites (e.g., Zr4+) can activate the dissociation of the hydroxyl groups sequently, the in-situ generated pentanoic acid can be converted
in alcohols for MPV reaction to produce an unstable intermediate to 5-nonanone with ketonization, followed by subsequent deoxy-
4-hydroxypentanoate, followed by intramolecular esterication or genation and oligomerization to produce nonane and C18C27
transesterication to yield GVL promoted by acid or base sites. alkanes, respectively. The decarboxylation of ring-opening product
Using formic acid as the hydrogen source, Deng et al. [798] state pentenoic acid leads to the formation of butene, which is able to
that the transformation of LA to GVL is achieved over a heteroge- be dimerized to C8 alkanes. By means of transesterication, alkyl
neous ruthenium based catalyst including RuP/SiO2, RuN/SiO2 pentenoate is yielded from GVL, which can be transformed into
and RuS/SiO2 in basic water with equimolar formic acid (Fig. 48; caprolactone, caprolactam, and adipic acid by hydroformylation,
Table 10, Entries 5255). The immobilized Ru2+ is speculated to act hydrocyanation, and hydroxycarbonylation, respectively. More-
as a bifunctional catalyst to decompose formic acid and hydroge- over, a precursor of acrylic polymers, -methylene--valerolactone,
nate LA in a single step, producing a high GVL yield of 96%. The only can be created from GVL by reacting with formaldehyde [820]. All
side products, water and carbon dioxide, are easily removed and of these reaction pathways demonstrate that GVL is a versatile plat-
separated from the product GVL under reduced pressure (Table 10, form for the production of chemicals and biofuels.
Entries 56 and 57) [799,800]. Similarly, Du et al. [801] developed Besides the complete catalytic hydrogenation of MF and furfu-
a hydrogen-independent reductive process for the conversion of LA ral to produce MTHF [821,822], GVL has recently emerged as a
and esters to GVL over supported gold catalysts, especially promising sustainable substrate as well [823]. A simple, yet versa-
Au/ZrO2(Table 10, Entries 58 and 59) [802]. Hydrophobic alcohols tile heterogeneous catalyst system comprised of highly dispersed
like butanol are able to be used for the intermediate production of copper in a zirconia matrix (Cu/ZrO2OG) prepared by an oxalate-
levulinate and formate esters and can be recovered by extraction gel-coprecipitation method is ecient to selectively catalyze the
protocol after elimination from the esters caused by the subse- hydrogenolysis of GVL in ethanol [824]. Both products 1,4-
quent formation of GVL. Afterwards, the same group describe an pentanediol and MTHF can be selectively produced by controlling
earth-abundant, inexpensive, and robust copper-based metal oxide the calcination temperature for Cu/ZrO2OG catalyst. A high MTHF
catalyst Cu/ZrO2 for the direct conversion of an aqueous mixture yield of 91% with a remarkable conversion of GVL (up to 98%) is re-
of LA and formic acid (1:1, n/n), giving GVL in high yields (up to 100%) alized at 240 C and 6 MPa H2 partial pressure within 6 h, when the
(Table 10, Entry 60) [803]. The use of formic acid produced during calcination temperature is set at 300 or 400 C. Under identical re-
acid hydrolysis of biomass provides in-situ generation of H2 gas in action conditions but increasing the calcination temperature to above
the system for the subsequent hydrogenation process. As com- 600 C, 1,4-pentanediol is observed to be the major product (76%
pared to platinum or palladium catalyst in the hydrogenation of selectivity) with a very poor selectivity to MTHF (11%) for GVL con-
ketones, ruthenium generally exhibits relatively lower activity in version of 96%. The H2 pressure and copper loading are also found
gas phase, but is ecient under aqueous/liquid phase conditions to affect the distribution of the products [825]. At a xed temper-
[815817]. The presence of an H-bonded water molecule has been ature of 265 C with 5 wt% Cu/SiO2 catalyst in the hydrogenation
veried to dramatically reduce the energetic span of the reaction of LA with a complete conversion, the selectivity toward GVL in-
pathway and to enhance catalytic activity [818]. Among various hy- creases from 94 to ~100% with an increase in H2 partial pressure
drogen sources used for GVL production, molecular hydrogen, formic from 0.1 to 1.0 MPa, while a further increase in pressure gives rise
acid and secondary alcohols are always demonstrated to exhibit high to the formation of 1,4-pentanediol at the expense of GVL. An in-
catalytic performance. However, high pressure is involved in the crease in copper loading leads to further hydrogenation of GVL to
storage/usage of hydrogen, which is expensive and unsafe. For using MTHF with a high yield of 64% at copper loading up to 80 wt%.
formic acid as the H-donor, only limited number of catalysts bearing Notably, the addition and the formation of water in the catalytic
acid-resistant property can selectively decompose formic acid into process of LA hydrogenation over Ru/C catalyst inhibit the
H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194 163

Fig. 49. Pathways for upgrading of -valerolactone (GVL) to biofuels and valuable chemicals. MTHF: 2-methyltetrahydrofuran. Adapted with permission from Ref. 819, Copy-
right 2010 American Chemical Society.

dehydration step and shift the dominant reaction toward the gen- produces pentanoic or valeric acid and its esters [833835]. The
eration of 2-pentanol (Fig. 50). In line with this, the desired product counterpart alkyl (mono/di) valerate esters are regarded as plat-
MTHF in a yield of 61% is obtained from LA via a two-step reac- form chemicals for cellulosic transportation fuels [836], which can
tion involving an intermediate removal of water [826]. be manufactured from lignocellulosic materials through the se-
In an aqueous solution at temperatures above 350 C and water quential hydrolysis to LA, hydrogenation of the organic acid to GVL,
partial pressure of 100 kPa, GVL reactant over a solid acid catalyst ring-opening and hydrogenation to valeric acid, and esterication
undergoes ring-opening to produce 3- and 4-pentenoic acids, and with alcohols (Fig. 52) [837]. In line with this, a cooperative mech-
succedent isomerization to form 2-pentenoic acid, followed by ir- anism of Pt and Bronsted acid sites of HMFI zeolite has been
reversible decarboxylation to yield 1-butene and carbon dioxide in proposed for the case of LA conversion to valeric biofuels, in which
an equimolar amount [827]. However, the isomerization of 1-butene the formation of alkyl valerate is driven by Pt-catalyzed hydroge-
to trans- and cis-2-butene essentially proceeds to equilibrium, and nation of LA to GVL, which undergoes proton-assisted ring-opening
only 23% of 1-butene in C4 stream is retained [828]. Unexpect- by the acidic zeolite, followed by Pt-catalyzed hydrogenation and
edly, almost pure 1-butene of C4 stream (>99%) is achieved with a acid-mediated esterication [838]. In particular, one-pot conver-
Lewis acid catalyst like -Al2O3 for the decarboxylation of GVL in sion directly from LA is realized over 1 wt% Ru/HZSM5 catalyst,
water at 275 C [829]. On the contrary, the decarboxylation of GVL and a moderate yield of valeric acid and its esters (46%) is ob-
under anhydrous conditions is correlated strongly with the Bronsted tained at 200 C and 4 MPa H2 partial pressure [839]. The GVL ring-
rather than Lewis acidity of the catalyst [830]. With an integrated opening step appears to be the rate-determining step on the pathway
biorening strategy [831], GVL can be produced simultaneously from to valeric acid, and the increase in acid sites on the support im-
the cellulose and hemicellulose fractions using GVL as solvent, which proves the selectivity to ethyl valerate and valeric acid [840]. As an
is converted to butene and then into butene oligomers in the pres- interesting alternative to noble metals, a bifunctional catalyst con-
ence of a number of acids and metal catalysts (Fig. 51) [832]. sisting of copper supported on an amorphous material with weak
In the presence of acid sites, the ring-opening reaction of GVL acidity (e.g., ZrO2SiO2) converts 90% GVL directly into pentyl val-
to pentenoic acid takes place easily, whereas further hydrogena- erate with a selectivity up to 83% at 250 C and 1 MPa H2 partial
tion rather than decarboxylation of the unsaturated carboxylic acid pressure after 20 h [841]. Without using an acidic support such as

Fig. 50. Schematic of MTHF (2-methyltetrahydrahydrofuran) and 2-pentanol formation in LA-to-GVL (levulinic acid-to--valerolactone) conversion.
164 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

Fig. 51. Schematic of butene oligomers produced from simultaneous conversion of hemicellulose and cellulose over acidmetal catalysts via LA (levulinic acid) and GVL
(-valerolactone). FfA: furfuryl alcohol. Adapted with permission from Ref. 832, Copyright 2013 Royal Society of Chemistry.

Cu/ZrO2SiO2, the Cu/SiO2 catalyst exhibits comparable activity (91% C18 alkenes, which is a precursor for jet fuel upon hydrogenation
conversion) and improved selectivity of 92% in the one-pot trans- [844]. Using different substrates (e.g., LA and cellulose) as starting
formation of GVL into pentyl valerate [842]. It is speculated that the materials, the appropriate combination of acids with metals through
small copper particles display catalytically relevant Lewis acidity integrated biorenery processes also produces corresponding hy-
which is increased with reduction of CuO phase to the metallic state drocarbon fuels via the key intermediate C9 ketone [845,846]. The
[842]. The subsequent conversion of valeric acid via ketonization production of bio-based polymers can be achieved from further
leads to the formation of 5-nonanone over niobia and/or a ceria upgrading of GVL to di-functional monomers, followed by copoly-
zirconia catalyst, and a diesel fuel n-nonane is produced from this merization [847852]. GVL, which has been identied as an
C9 ketone through successive hydrogenation and dehydration to a important precursor, is being extensively used for the production
mixture of linear C9 alkenes, followed by a second time hydroge- of chemicals and fuels on the lab scale and it is likely to nd at-
nation [843]. By another way, the oligomerization of C9 alkenes can tractive applications in industrial manufacture in the near
occur at 160 C over an acid catalyst such as Amberlyst-70 to produce future.

Fig. 52. Routes to the valeric biofuels from lignocellulosic materials involving levulinic acid (LA) and -valerolactone (GVL). Adapted with permission from Ref. 837, Copy-
right 2010 Wiley-VCH.
H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194 165

Fig. 53. Possible reaction pathways for the formation of cyclopentanol and 3-hydroxymethylcyclopentanone from furfural and HMF (5-hydroxymethylfurfural), respectively.
Adapted with permission from Ref. 868, Copyright 2014 Elsevier.

4.2.5. Hydrogenation/hydrodeoxygenation of biomass derivatives to water is mainly converted into cyclopentanone at yields of up to
other hydrogenated products 77% over 5wt% Pt/C catalyst at 160 C and 8 MPa H2 partial pres-
Bifunctional materials have been used to prepare a number of sure along with a small amount of cyclopentanol (5% yield) [869]
other products via hydrogenation-involved processes. For example, generated from further hydrogenation of cyclopentanone [870]. The
acidmetal binary catalysts mediated selective hydrogenation of MA attack of a H2O molecule on the 5-position of FfA contributes to the
to succinic anhydride or propionic acid [853855], reduction of LA opening and closure of the furan ring, and to the high selectivity
to diols, alkenes or alkanes [856858], reductive amination of LA of cyclopentanone that is closely related to the presence of
to pyrrolidones [859], hydrogenolysis of diethyl succinate to THF 2-cyclopentenone [871]. The stabilization of the carbocation of FfA
[860], and selective H2 synthesis from carbohydrates [861,862] have produced in an excess of hydrogen by the favorable scission of the
great potential for producing hydrogenated products derived from CO bond in the alkoxide or hydroxyalkyl intermediates seems to
biomass. inuence the selectivity of subsequent reactions [872]. Further-
more, the rate balance between the formation of FfA polymers on
4.2.5.1. Cyclopentanone and 3-hydroxymethylcyclopentanone. Cyclo- the catalyst surface and their decomposition also results in the high
pentanone, which is a versatile intermediate for the synthesis of selectivity of FfA rearrangement to cyclopentanone [873]. Similar-
rubbers, fungicides, pharmaceuticals, avors, fragrances, and C15C17 ly, the ring rearrangement of HMF to a cyclopentanone derivative,
diesel or jet fuels [863865], is generally prepared from petroleum- 3-hydroxymethylcyclopentanone, can be achieved through the hy-
based products via the vapor-phase cyclization of 1,6-hexanediol drogenation with metal nanoparticles and the Lewis acid catalysis
[866] or the liquid phase oxidation of cyclopentene [867]. However, of metal oxide supports (Fig. 53, Route B) [874], and a highest
selective rearrangement of FfA to cyclopentanone can be realized 3-hydroxymethylcyclopentanone yield of 86% is obtained over Au/
with the promotion of hydrogen ions created by self-dissociation Nb2O5 catalyst at 140 C and 8 MPa H2 partial pressure within 12 h.
of water (Fig. 53, Route A) [868]. Namely, cyclopentanone as the ex- By taking advantage of the selective hydrogenation on metal par-
clusive product forms in a high yield of 95% over metal catalysts ticles and the Lewis acid catalysis of solid supports, HMF can be
with a low metal concentration of 0.251.0 wt% at 0.82.5 MPa H2 selectively converted into 3-hydroxymethylcyclopentanone. For fur-
partial pressure. In contrast, relatively higher hydrogen partial pres- fural, the balance between the rates of formation of furfuryl alcohol
sures and catalyst concentrations favor the formation of THFA. When polymers on the catalyst surface and their decomposition is likely
furfural is selected as the substrate, an additional hydrogenation step to be responsible for the high selectivity of furfural rearrange-
is required for the production of hydrogenated intermediate FfA. ment to cyclopentanone.
In an organic solvent like n-butanol, n-decanol and THF, the main
products of the reaction are the hydrogenated derivatives of fur- 4.2.5.2. Diols. In the liquid-phase hydrogenation of FfA, THFA is gen-
fural such as FfA, THFA, MF, and MTHF, while furfural dissolved in erally the dominant product [875], while harsh reaction conditions
166 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

tend to drive the hydrogenolysis of the furan ring to synthesize diols selectivity to FfA is obtained over Cu/SiO2, but with only small
such as 1,2-pentanediol, 1,5-pentanediol, and 1,4-pentanediol. In the amounts of 2-methyl furan formed at high reaction temperatures
case of 1,2-pentanediol, low pressure and high temperature favor (ca. 290 C). In strong contrast, furan is mainly produced from the
its generation, in which water is found to signicantly enhance the conversion of furfural by decarbonylation over Pd/SiO2, which is
reaction rate [876]. Moreover, the cooperative catalysis of metal capable of further reacting with hydrogen to give THF. For Ni/SiO2
nanoparticles and a basic support like HT drastically increases the catalyst, ring opening products such as butanal, butanol and butane
selectivity for 1,2-pentanediol [877]. However, a one-pot two-step are observed in signicant amounts [894]. Besides pentane, lighter
process with controlled temperatures is benecial for the synthe- alkanes including C1, C2, C3, and C4 were also detected, which might
sis of 1,5-pentanediol from furfural over bimetallic catalysts such depend on the relative rates of CC bond cleavage, dehydration and
as PdIrReOx/SiO2, RhIrReOx/SiO2 and Pt/Co2AlO4, in which the hydrogenation reactions [895]. Notably, C6 alkane in minor per-
lower-temperature reaction step is very crucial for the total hydro- centages is observed in the products and was probably formed
genation of furfural into THFA intermediate and the hydrogenolysis through FT reactions [896]. Likewise, an aqueous-phase HDO of sor-
occurs during the high temperature step [878880]. An integrated bitol to the gasoline-range products including C5C6 alkanes, C2C6
conversion of furfural to 1,4-butanediol with a yield of 85% has been alcohols, THFs, tetrahydropyrans, and small amounts of C2C6 al-
realized over a multifunctional Pt/TiO2ZrO2 catalyst with H2O2 in dehydes, ketones and organic acids could be realized in a continuous
HCOOH/H2O/MeOH at 120 C and 3.5 MPa H2 partial pressure after ow reactor [897]. It was found that the gasoline-range yields on
6 h. The conversion involves two sequential reaction steps consist- Pt/ZrP and PtReOx/C were 67% and 44%, respectively. With respect
ing of selectively oxidizing furfural to furanones and hydrogenation to the distribution of products, PtReOx/C had a higher CO2 selec-
of the mixture of furanones to 1,4-butanediol [881]. Likewise, the tivity than Pt/ZrP, suggesting the PtReOx/C showed a higher rate
production of 1,3-propanediol and 1,6-hexanediol has been real- of decarbonylation than Pt/ZrP, while Pt/ZrP had a higher rate
ized from the hydrogenolysis of glycerol and HMF over metal of CO bond cleavage than PtReOx/C, leading to a higher C6 product
particles with an acidic support, respectively [882,883]. In com- selectivity (36% vs. 12%). With sorbitol as intermediate [898], a metal
parison with Bronsted and Lewis acidic supports like ZrP, HY zeolite, acid binary catalyst system composed of {IrReOx/SiO2 + HZSM-5}
Nb2O5, HZSM-5, SiO2Al2O3, Al2O3 and SO4/ZrO2, the specic Bronsted is effective in the one-pot conversion of cellulose in H2O/n-dodecane,
acidity on ZrP support can effectively accelerate the cleavage of CO giving n-hexane yields of 83% and 78% from ball-milled cellulose
bond in a furan ring, while the presence of a transition metal is re- and microcrystalline cellulose, respectively [899]. The yield of
sponsible for FA dissociation, hence supplying in-situ the required n-hexane remains above 70% even when ball-milled cellulose at a
hydrogen for hydrogenation. water weight ratio of 1:1 is used. The hydrolysis of cellulose to
glucose via water-soluble oligosaccharides catalyzed by protons pro-
4.2.5.3. Upgrading of bio-oil. Bio-oil produced from biomass through duced from HZSM-5 or hot water is considered to be the rate-
ash pyrolysis and hydrothermal liquefaction can be upgraded to determining step. In a more fast reaction rate, glucose can
engine fuels via HDO and zeolite cracking [884886]. In the process be hydrogenated to sorbitol over IrReO x /SiO 2 , followed by
of syngas conversion to hydrocarbons, FischerTropsch (FT) syn- hydrogenolysis over IrReOx/SiO2 and HZSM-5 to produce the end
thesis is considered as a crucial step, while the biggest challenge product, n-hexane.
is the control of selectivity [887,888]. In this regard, the combina- The use of extractive solvents like alkylphenol to separate GVL
tion of acidic zeolites with an active FT catalyst considerably increases from sulfuric acid following the LA hydrogenation step is an essen-
the product selectivity toward liquid hydrocarbons [889]. As a model tial step for butene oligomerization [900]. The conversion of GVL
reaction for bio-oil upgrading, a one-step hydrogenation to aromatic hydrocarbons takes place over a zeolite catalyst at 500 C,
esterication of furfural with acetic acid over a bifunctional catalyst and gives a carbon yield of 57% of aromatics from GVL with HZSM-5
5 wt% Pd/Al2(SiO3)3 or Pd/AlSBA-15 proceeds under mild condi- (Si/Al: 25) catalyst [901]. To increase the length of carbon chains,
tions to give FfA and ester in a selectivity of 66% [890,891]. Synergistic coupling and condensation reactions are involved [902,903]. Liu et
effect of metal sites and acid sites for the one-step hydrogenation al. [904,905] developed an integrated catalytic process for the con-
esterication over composite bifunctional catalyst of 5% Pd/ version and upgrading of biomass feedstocks like fructose into 5,5-
Al2(SiO3)3 is more ecient than the corresponding physically mixed dihydroxymethyl furoin (DHMF), through self-coupling of HMF via
monofunctional catalysts. In a similar manner, Hf-, Zr- or Sn-Beta organocatalysis with a N-heterocyclic carbene, and subsequently into
zeolites effectively catalyze the coupled transfer hydrogenation and n-C12H26 alkane over a bifunctional catalyst system consisting of {Pd/
etherication of HMF with primary and secondary alcohols into re- C + acetic acid + La(OTf) 3 } via metalacid tandem catalysis. In
newable fuel additives 2,5-bis(alkoxymethyl)furans without using particular, the third step HDO of DHMF is carried out with metal
an external hydrogen source or precious metals [378,892]. Among (Pd/C)acid (La(OTf)3) catalyst in acetic acid to afford 78% alkanes
these zeolites, Hf- and Zr-Beta appear to be more active in the MPV with a 64% selectivity to n-C12H26 at 250 C and 2.1 MPa H2 partial
reduction whereas Sn-Beta exhibits the highest stability and se- pressure for 16 h. In combination with dehydration, aldol-
lectivity toward etherication. condensation/hydrogenation, and dehydration/hydrogenation
processing, Chheda and Dumesic [906] demonstrated the possibil-
4.2.5.4. Alkanes. Renewable routes have been developed to produce ity of converting carbohydrate feedstocks to produce liquid alkanes
liquid alkanes from biomass derivatives. The aqueous phase cata- (Fig. 54). Initially, the catalytic hydrolysis reaction involves break-
lytic hydrogenation/dehydration of furfural produces pentane over ing COC linkages to form simpler carbohydrate molecules at high
bifunctional nickel-based catalysts [893]. On the nickel active sites temperatures in the presence of acids. The resulting soluble car-
of these catalysts, some hydrogenated intermediates such as FfA, bohydrates could subsequently undergo acid-mediated dehydration
THFA, 1,5-pentanediol, and tetrahydro-2-furancarboxaldehyde to produce furanic compounds (e.g., HMF and furfural) through loss
derived from furfural, followed by migration to acid sites of the bi- of three water molecules at moderate temperatures of 100
functional catalyst and undergo dehydration to form alkenes, and 200 C. The subsequent aldol-condensation involving the CC
in the subsequent hydrogenation step saturate the C:C bonds of coupling between two compounds containing carbonyl groups is
pentene to give pentane. The product distributions are greatly af- capable of forming larger organic molecules, which is generally
fected by the type of metals with respect to the interaction strength carried out over base catalysts at low temperatures in polar sol-
of the furan ring with the metal surface and the type of surface in- vents like water and watermethanol. Finally, the hydrogenation step
termediates stabilized by each metal [894]. Specically, high could saturate the C:C and C:O bonds of the aldol-adducts over a
H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194 167

Fig. 54. Schematic diagram for production of liquid alkanes from sugars in biorenery. Adapted with permission from Ref. 906, Copyright 2007 Elsevier.

metal catalyst, thus forming large water-soluble organic com- the ketone [909]. Deutsch et al. [910] found that the dehydration
pounds, followed by repeated dehydration and hydrogenation of cyclohexanol derivatives was the rate limiting step in produc-
reactions catalyzed by bifunctional materials containing acid and ing cyclohexane derivatives in the deoxygenation of phenols over
metal sites to produce liquid alkanes in a four-phase reactor system. a copper chromite catalyst via hydrogenation, dehydration and hy-
Dedsuksophon et al. [907] reported that 1520% maximum yields drogenation. Likewise, the combination of noble metals (Ru, Rh and
of C5C15 could be detected from tapioca our and corncobs through Pt) supported on Al2O3 (or C) with solid acid zeolites tested for HDO
three sequential steps involving WO3ZrO2 catalyzed hydrolysis/ activity of the oligomeric technical lignins predominantly contain
dehydration at 300 C for 5 min, aldol-condensation of HMF or 8O4 inter-unit linkages, to give 3560% conversions of lignin with
furfural with acetone at 80 C within 30 h, and hydrogenation over 6570% product selectivity for aromatic hydrocarbons such as toluene
supported Pd particles at 120 C after 6 h in a single pot. Notably, at 250 C and 45 MPa for 812 h [911]. Specically, high yields of
the yields of hydrocarbon compounds increase with an increase in toluene (up to 100%) are obtained from the HDO of dibenzyl ether
reaction temperatures from 80 to 120 C, but decrease at higher re- at 250 C and 10 MPa H2 partial pressure for 2 h when a sup-
action temperatures of 150 and 180 C, which is possibly due to ported FeS2 catalyst is used [912]. The chemical transformation of
further conversion or cracking of water-soluble organic compounds. FeS2 into Fe(1x)S has been demonstrated to be responsible for the
high activity and selectivity gained in the conversion of dibenzyl
4.2.5.5. Cycloalkanes. Lignin-derived components are commonly used ether into toluene.
as model chemicals for HDO to investigate possible reaction path- The one-pot dehydroxylation of phenols to arenes like benzene
ways and susceptibilities dominated by several typical oxygen can be realized by catalytic tandem reactions with 2-propanol as
functionalities including hydroxyl groups bound to aromatic and ali- an H-donor and concurrent use of Raney Ni and H-Beta-35 (Fig. 55)
phatic carbons and methoxy groups in phenolic compounds [908]. [913]. The production of low boiling point arenes instead of high
A large number of studies on hydrogenation/hydrogenolysis of simple boiling phenols from lignin can greatly facilitate the valorization of
aromatic compounds have been carried out, so as to facilitate the lignin products by conventional renery processes. Through a cleav-
valorization of lignin. For instance, the direct hydrogenation of phenol age of CO bonds in phenolics followed by an integrated metal- and
to cyclohexanone is always hindered by over-reduction to acid-catalyzed hydrogenation and dehydration, cycloalkanes-
cyclohexanol, while the introduction of Lewis acid sites can se- containing transportation biofuels (>90% selectivities) are synthesized
quentially enhance the hydrogenation of phenol to cyclohexanone from the full HDO of lignin-derived phenolic monomers and dimers
over palladium nanoparticles and inhibit further hydrogenation of over a bifunctional catalyst of Ru supported in HZSM-5 at 200 C
168 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

Fig. 55. Proposed main reaction pathway and overall reaction for the dehydroxylation of phenols to arenes by catalytic tandem reactions with concurrent use of Raney Ni
and H-Beta-35 catalysts. Adapted with permission from Ref. 913, Copyright 2013 Wiley-VCH.

and 5 MPa H2 partial pressure after 4 h [914]. However, issues on hydrogenation of glucose to sorbitol or 2-deoxysorbitol, and oxi-
the recycling of catalysts for complex catalytic systems at relative- dation of sorbitol to fructose and sorbose can be realized via electro-
ly high temperatures (200250 C) are not commonly studied and catalytic processes [943946]. In parallel, electro-oxidative cleavage
it is likely that the structure of these heterogeneous catalysts of lignin is likely to be achieved through disruption of biphenyl link-
becomes deactivated with time due to the formation of chars or ages (a), diphenylether linkages (b), dibenzylether linkages (c), -O-4
humins and adsorption on the catalytic surfaces. linkages (d), -5 linkages (e), linkages (f) and -1 couplings (g)
(Fig. 56) [947], and further upgrading of the lignin monomers is pos-
5. Other bifunctional materials and catalytic routes sibly through electrocatalytic hydrogenolysis/hydrogenation [948].
The coupling of sequential electrocatalytic processes generally in-
Catalytic transformation of biomass into chemicals products via volving degradation of biopolymers to small molecules and
chemical routes has been reviewed and analyzed [915], and updated subsequent hydrogenation/oxidation appears to be one of e-
in follow-up studies [916918]. Fuel cells coupled with biomass- cient ways for the direct transformation of biomass resources into
derived fuel processors are able to provide renewable energy and biofuels and value-added chemicals.
chemicals in a CO2-neutral manner [919]. Electrocatalytic oxida- In comparing the upgrading of biomass-derived platform mol-
tion of glucose has been extensively studied, since this reaction has ecules with heterogeneous catalysts, electrochemical catalysis offers
applications in glucoseair fuel cells as well as in medical and food relatively high selectivity of products and increased reaction rates.
industries as glucose sensors [920924]. In electrochemical catalysis, the electrode potential and the Fara-
daic current are two additional external control parameters that allow
5.1. Metals (Au, Ag, Cd, Ru, Pt, Pd, Cu, Ni) dispersed into nano-sized tuning of the thermodynamic driving force and activation energy
particles [949]. Over supported metal nanoparticles (e.g., Au and Pd), the
electrocatalytic oxidation of HMF in alkaline media was able to se-
Gold dispersed into nano-sized scale particles or alloyed with lectively produce FDCA at high selectivity giving trace amounts of
other metals normally has high stability and enhanced activity in DFF [950], while the corresponding hydrogenation reactions give
electrocatalytic glucose oxidation [925930], in which gluconic acid BHMF, BHMTF or even DMF in neutral or acidic solutions [951953].
can be the nal product [931]. Noble metals like Ag, Cd, Ru, Pt, and For furfural, attention has been paid to electrocatalytic reduction
Pd have been developed for this catalytic process [932935], while to synthesize the dominant product FfA in different reaction media
more attention has been paid to non-precious metal (e.g., Cu and [954957], and THFA, MF and MTHF are found to form in a con-
Ni) catalysts [936939]. Carbohydrates including mannose, galac- tinuous electrocatalytic membrane reactor [958]. When substrate
tose, fructose, arabinose and xylose can be detected through is selected as LA, the electrocatalytic hydrogenation in parallel with
electrocatalytic oxidation [940942], and some interesting sugar the heterogeneous bifunctional catalysts-mediated chemical process
transformations such as simultaneous production of xylitol and produced GVL or valeric acid in high yields [959962]. Likewise, a
xylonic acid from xylose, isomerization of lactose into lactulose, series of organic acids or aldehydes can probably be produced from
H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194 169

Fig. 56. Schematic of the lignin structure with (a) biphenyl linkages, (b) diphenylether linkages, (c) dibenzylether linkages, (d) -O-4 linkages, (e) -5 linkages, (f) link-
ages, and (g) -1 couplings. Adapted with permission from Ref. 947, Copyright 2012 Royal Society of Chemistry.

electrocatalytic oxidation of biomass derived alcohols such as ethanol, can be coupled with fuel cell to provide renewable energy in the
ethylene glycol, and glycerol [963968]. future.
The combination of biocatalysis with inorganic catalysis is a
5.2. Cascade reactions with enzymes and electrocatalytic methods method for one-pot conversion of biomass-related feedstocks [978].
Vennestrm et al. [979] provide examples on combined enzyme and
Combining an enzyme, oxalate oxidase, with an organic oxida- chemical catalysts for the production of commodity chemicals from
tion catalyst, 4-amino-TEMPO can allow the complete electrochemical renewable feedstocks. In the case of oxidase enzymes-mediated re-
oxidation of the biofuel glycerol to CO2 (Fig. 57) [969]. In this hybrid actions, oxygen was reduced to hydrogen peroxide. Pyranose oxidase,
cascade process, TEMPO-NH2 catalyzes the oxidation of glycerol to which is an oxidase enzyme, catalyzes the oxidation of aldopyranoses
mesoxalic acid, while a combination of oxalate oxidase and TEMPO- to form 2-keto sugars and H2O2 [980], and a combined chemical hy-
NH2 transforms mesoxalic acid to glyoxalic acid, oxalic acid, and nally drogenation as a second step is capable of producing fructose from
CO2. Importantly, CO2 possibly captured from the ambient air [970] glucosone (2-keto sugar) [981]. In fact, isomerase is able to sepa-
might be able to be directly employed in biomass processing [971] rately realize the glucose-to-fructose conversion [982,983]. An
or hydrogenated to form a range of carbon-rich fuels like CO, oxalate, integrated enzyme cascade-chemocatalytic transformation of cel-
formic acid, and methanol via electrochemical catalysis [972974]. lulose oligomers into HMF (up to 46% yield) has been achieved in
The production of hydrogen can also be realized from water elec- aqueous (enzyme) and organic (chemical) media with enzyme and
trolysis or reforming of renewable chemicals such as glucose and acid functionalized mesoporous silica nanoparticles (MSNs), re-
ethanol [975977]. Many types of biomass-derived fuels (e.g., ethanol, spectively (Fig. 58) [984]. The catalytic process generally involves
biodiesel and biogas) as well as bio-based chemicals (e.g., HMF, glyc- thermophilic glucose isomerase enzyme for glucose isomeriza-
erol and LA) can be used as the feedstock for a fuel processor that tion to fructose and an acid catalyst for fructose dehydration to HMF

Fig. 57. Possible electrocatalytic cascade oxidation of glycerol by TEMPO (2,2,6,6-tetramethyl-piperidin-1-oxyl)-NH2 and oxalate oxidase (OxO). Adapted with permission
from Ref. 969, Copyright 2014, American Chemical Society.
170 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

Fig. 58. An integrated enzyme cascade-chemocatalytic conversion of cellulose into HMF (5-hydroxymethylfurfural) in a biphasic system with enzyme and acid functionalized
MSNs (mesoporous silica nanoparticles). Adapted with permission from Ref. 984, Copyright 2014 Wiley-VCH.

[985,986]. After further introduction of an HMF/furfural oxidore- by acetoacetate decarboxylase from Clostridium acetobutylicum [994].
ductase into the catalytic systems, FDCA and furoic acid are formed In this catalytic system, mediators such as methyl viologen and 2,2-
from hexoses and pentoses, respectively [987989]. HMF and fur- azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) are capable of
fural can be successively hydrogenated into BHMF and FfA through accepting the overcrowded electrons around carboxylate group of
anaerobic biotransformation by using the aldehyde (CHO) as an LA and of assisting spontaneous electron ow from - to -carbon.
electron acceptor [990,991]. Biotransformation appears to enhance Through corresponding chemo-enzymatic catalysis, biorenery prod-
overall metabolic capacity of other anaerobic bacteria (e.g., sulfate- ucts like methyl ethyl ketone, methane, polyhydroxyalkanoates,
reducing bacteria and acetogenic bacteria) in anaerobic digestion xylogluco-oligosaccharides, and starch can be produced from non-
processes, demonstrating that synergetic effects exist among dif- edible biomass [9951000]. The combination of chemical and
ferent enzymes. The introduction of chemo-catalytic methods can enzymatic catalysis can be used to integrate cascade reactions in
play a valuable role in both upstream and downstream processing a single pot, thus avoiding the separation of intermediates from the
of biomass by improving eciency and selectivity of target products. reaction mixtures and maintaining the separate advantages of the
Chemo-enzymatic routes have been developed to produce other two different catalytic systems for ecient biomass transformations.
biomass-derived chemicals. For instance, GVL can be produced from Photocatalysis shows good potential for transformation of lig-
LA with an integrated bioprocessing system involving the produc- nocellulosic biomass to valuable products [1001]. The rapid
tion of intermediate 4-hydroxyvaleric acid from LA with an elucidation of reaction routes mediated by functional catalytic ma-
intracellular enzyme P. putida, and subsequent lactonization that terials can widen the scope of biomass transformations.
occurs extracytosolically in acidic medium (Fig. 59) [992]. In a 2 L
bioreactor, the production of 4-hydroxyvalerate and GVL from 6. Auxiliary processes to boost catalytic eciency
levulinate have been examined, and titers of 27.1 g L1 and 8.2 g L1
are achieved for the two respective compounds. Immobilized lipase In multi-catalytic processes involving biomass conversion, cat-
B from Candida antarctica not only afforded a high yield of GVL (90%) alyst selectivity, on some level, is a function of the ratio and
from LA via EL as intermediate promoted by Amberlyst-15, but also distribution of active sites for both heterogeneous and homoge-
exhibits a remarkable enantiomeric excess of the desired (S)-GVL neous reactions. For the case of LewisBronsted acid-mediated
(>99% ee) [993]. In the overall process, catalyst recycle is possible hydrolysis and dehydration processes, presence of Lewis acid sites
especially in the case of Amberlyst-15 and C. Antarctica. Moreover, responsible for sugar isomerization is necessary to accelerate the
organic solvents used in the extraction or reaction can be reused thermokinetic performance. However, catalysts with excess of Lewis
after distillation, leading to an overall decrease in waste produc- acid sites often lead to a decrease in product selectivity that is as-
tion. Starting from the same substrate LA, 2-butanone is obtained sociated with the formation of humins [1002,1003]. Therefore,

Fig. 59. Integrated bioprocessing system for the production of GVL (-valerolactone) from LA (levulinic acid). PON1: paraoxonase I.
H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194 171

Fig. 60. In-situ catalytic hydrolysis of air-preoxidized-cellulose to glucose. Adapted with permission from Ref. 1032, Copyright 2014 Royal Society of Chemistry.

suitable adjustment of active site distribution is one of the key issues oxygen, which can dissolve lignin and loosen the remaining hemi-
in realizing high product selectivity. Several other factors like re- cellulose from insoluble crystalline cellulose, have gained increasing
action media, diffusion limitations, and hydrophobic/hydrophilic interest [10281030]. For example, sugarcane bagasse pretreated
environment of the solid catalysts are also important in determin- in combination of dual metal salts such as MnSO4H2O and ZnO with
ing the performance of catalytic systems [1004]. In these past few H2O2 allows cellulose recovery and delignication, thus enhanc-
years, much attention has been paid to developing integrated cata- ing the downstream ethanol production [1031].
lytic processes for direct conversion of waste biomass, algae, and
energy crops into desired compounds like food, proteins, sugars, poly- 6.1.2. Preoxidationhydrolysis
mers, platform chemicals, and liquid fuels. Nevertheless, solid Two-step preoxidationhydrolysis strategy can transform cel-
solid interactions between biomass and solid catalysts are necessary lulose into glucose (Fig. 60), in which the hydroxymethyl group is
for the lignocellulose substrates to degrade. As such, coupling pre- rst oxidized to a carboxyl group by preoxidation treatment using
treatment processes with suitable auxiliaries like heating modes may air as an oxidant, and reduction of the polymerization degree of cel-
boost biomass valorization. lulose as well as the subsequent cellulose-to-glucose hydrolysis is
realized with the in-situ generated acid sites [1032]. The combi-
6.1. Biomass pretreatment nation of chemical or biological pretreatment with irradiation
including microwave, ultrasound, gamma-ray, and electron beam
Biomass pretreatment can breakdown or weaken the tight link- can provide more ecient results than a single pretreatment method
ages among cell-wall components of lignocellulosic biomass, thus that only possesses limited specic functioning mode and intrin-
enhancing its degradation in subsequent upgrading stages sic disadvantages. In this case, alkali pretreatment integrated with
[1005,1006]. Typical physical pretreatment methods are milling, chip- ultrasound or microwave is able to enhance the removal of lignin
ping, grinding and thermal treatment that decrease particle size and from lignocelluloses [10331035]. Similarly, ultrasound-promoted
crystallinity of biomass, but consume much energy [1007]. Biolog- IL pretreatment [1036] and acid catalyzed steam treatment [1037]
ical pretreatment can enhance delignication and enzymatic can increase the digestibility of lignocellulosic biomass. Other related
digestibility of lignocellulosic substrates, while it is time-consuming techniques for treating a broad range of biomass feedstocks for the
and expensive [10081010]. For the case of chemical pretreat- production of biofuels are provided in a review [1038].
ment, acid-catalyzed processes are capable of increasing the porosity
of substrates through breakage of covalent bonds, hydrogen bonds, 6.2. Reaction media
and van der Waals forces in biomass [1011,1012], while alkali can
destroy linkages between lignin and carbohydrates by saponica- Lignocellulosic biomass is mainly nonmelting solid material before
tion of intermolecular ester bonds [1013]. However, these two decomposition and charring occur in thermocatalytic processes. As such,
processes are usually accompanied with equipment corrosion, for- it is necessary to use a suitable reaction medium for controlled depo-
mation of side products, and issues in the recovery and recycle of lymerization of lignocelluloses, as well as for subsequent upgrading of
acids and bases. solventsoluble components and stabilization of products. Water is po-
tentially a green and cheap solvent for the conversion of biomass to
6.1.1. Molten salt hydrates and dual metal salts specic products although most biopolymers have low solubility in
Molten salt hydrates including ZnCl2, CaCl2, and LiCl are able to water [10391041]. However, water at high temperatures (ca. 250 C)
convert cellulose and hemicellulose into monosaccharides at mild or at supercritical conditions (>375 C, >22.1 MPa) can enhance the deg-
conditions in water, wherein the strong interaction between the ionic radation of biopolymers despite selectivity is typically low [10421045].
species and hydroxyls promotes cleavage of the hydrogen-bonding For the dissolution, fractionation and valorization of lignocellulosic
network [1014]. Traditional solvents like cadoxen/water, DMSO/ biomass components, ILs are considered to be promising candidates
tetrabutylammonium uoride, NaOH/urea, and LiCl/DMA can be used [10461049]. Particularly, metal chlorides in chloride-based ILs are
either for biomass pretreatment or directly for cellulose dissolu- robust catalytic systems for ecient conversion of cellulose, hemicel-
tion [10151018], but these solvents have several drawbacks such luloses, and lignin [1050]. In the case of transformation of sugars to
as volatility or generation of toxic gases and the need for multi- furanic compounds in ILs, the presence of Cl ions can promote the for-
step and prolonged process operations. Due to their low vapor mation of the 1,2-enediol from the acyclic form of sugars, resulting in
pressure and high solvation capacity, ILs have attracted much at- a signicant improvement of catalytic activity [1051,1052], while metal
tention for the homogeneous processing of lignocelluloses cations play role in sugar isomerizations to facilitate succedent dehy-
[10191023]. Some challenges such as high solvent cost, limited toxi- dration [1053]. Adding a certain amount of water into ILs-mediated
cological data, and regeneration requirements of ILs still remain to reaction media seems to raise the hydrolysis eciency of biopoly-
be addressed before they can be widely used in biomass valoriza- mers, thus increasing the yields of furan-type compounds, but too much
tion processes [10241027]. water promotes rehydration of products [10541056]. Likewise, the ad-
Chemical pretreatment of biomass has been widely studied. In dition of DMSO lowers the high viscosity of ILs to facilitate the mass
particular, some chemical agents like peroxides and high pressure transfer between the catalyst and substrate without affecting solubility
172 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

of biopolymers [10571059], and also enhances the stability of (1) combination of several types of active sites within a unique
mono-saccharides [1060] and products such as HMF and EMF solid catalyst that are incompatible in a homogeneous phase;
[1061,1062]. However, other high boiling organic solvents such as DMA (2) combination of complex transformations in a single pot
and N,N-dimethylformamide are not so selective for the desired prod- process;
ucts, and metal chlorides are required for DMA [10631065]. An NMR (3) implementation of cascade reactions and multistep conver-
study showed that DMSO is likely to act as a catalyst besides a solvent sions; and
for fructose-to-HMF dehydration at 150 C via an intermediate (4R,5R)- (4) elimination of intermediate separation and purication steps.
4-hydroxy-5-hydroxymethyl- 4,5-dihydrofuran-2-carbaldehyde [1066].
The functional IL 1-hydroxyethyl-3-methylimidazolium tetrauoroborate There are a number of common characteristics of the catalytic
used as a catalyst, rather than as solvent can directly promote glucose materials such as porosity and surface polarity important in cata-
dehydration in DMSO, giving HMF in yields as high as 67% at 180 C lyst design that discussed in the next sections.
within 1 h [1067]. In contrast, SO3H-functionalized ILs in water or ethanol
will lead to the formation of LA or EL from sugars via HMF or EMF re- 6.3.1. Porosity
hydration, respectively [10681070]. As an effective way to improve LA Porosity of solid materials directly affects surface area. Porous
yields, metal salts like NaCl and KCl can interrupt the hydrogen bonding materials that have high surface areas with highly accessible active
network of cellulose at high temperatures and pressures, thus facili- sites are crucial for substrate sorption and high activity. In general,
tating hydrolysis, dehydration, and rehydration processes [1071]. most of the catalytic sites of porous materials are located inside the
Moreover, the subsequent esterication of LA with long chain alco- pore system, and the reaction selectivity can be controlled because
hols can facilitate the separation of product for reuse of ILs [1072]. of the size limitation between pores and reagents, products or
In the context, ILs and DMSO are two important reaction media transition-states [1104]. It seems that the best choice for catalytic
to control or increase the selectivity of products especially furanic processes of large molecules is mesoporous and macroporous ma-
compounds. Nevertheless, ILs are still expensive and have limited terials [1105]. Unlike micropores which hinder the contact of
applications in scale-up processes for biomass, while DMSO which substrate and active sites, if pores are too large to offer the steric
has a high boiling point of 189 C requires much energy in its sep- restrictions, it will reduce the transition-state selectivity. Careful se-
aration from the products. As such, organic solvents with a moderate lection of functionalized materials and tailoring of the pore sizes
volatility seem to be promising alternatives [1073,1074]. In a mono- are necessary to overcome the mass transfer limitations in the pro-
phasic THFwater system, increased reaction performance, for either cessing of polymeric species. Ordered porous materials such as metal
furans or for LA is observed [10751078]. Notably, the increase of oxides and carbonaceous materials with narrow pore size distri-
electrical conductivity of water to THF can be achieved with the dis- bution show enhanced selectivity in some cases for sugar and lignin
solution of a small amount of ionic material like NaCl, rendering chemistry [1106,1107]. Metal oxides are not resistant to aqueous
the formation of a biphasic system that will promote the in-situ sep- reaction media, while they are stable on carbon supports with ex-
aration of products like HMF and furfural from aqueous mixture clusive micropores that appear to be unsuitable for conversion of
[10791081]. Other organic solvents such as toluene, MIBK, ace- polymeric biomolecules. Biomass-derived mesoporous carbons with
tonitrile, alcohols, and their mixtures have also been widely utilized well-dened pore architecture are preferable for applications in the
as extractive phases [10821087]. Among them, the use of water- catalytic conversion of biomass [1108,1109]. Modied zeolites and
miscible solvents as organic phase is expected to dissolve HMF better metal-organic frameworks (MOFs) with well-tailored pore sizes and
than common non-water-miscible solvents. Biomass-derived sol- active sites are promising candidates [11101113].
vents like MTHF, alkylphenols and GVL have been proposed as
sustainable co-solvents or extraction solvents [10881090]. In par- 6.3.2. Surface polarity
ticular, GVL with water used as the reaction medium can mediate Catalytic transformation of biomass via multiple steps may se-
the formation of monosaccharides, furfural, HMF, and even GVL di- quentially involve hydrophilic and hydrophobic molecules. Therefore,
rectly from corresponding biomass derivatives [10911094]. It is the proper adjustment of the adsorption and desorption pro-
interesting to note that solvent or catalyst may act as a reagent to cesses between active sites and reagents is necessary to optimize
directly inuence product distributions. Considering LA upgrad- the overall catalytic performance [1114]. Normally, the surface po-
ing in dimethylcarbonate as an example, K2CO3 can catalyze the larity of solid materials is affected by their own surface groups such
formation of methyl levulinate through methylation, as well as the as hydroxyl, carbonyl, carboxyl, alkyl, ether, and ionic species. In most
subsequent dimethylketal to produce dimethyl succinate at 200 C cases, functional materials with hydrophilic surfaces can facilitate
after 4 h [1095]. In this catalytic process, dimethylcarbonate is not the access of the substrates bearing many hydroxyl groups and the
only a solvent but also a reagent under a basic condition. Either HCl desorption of the hydrophobic products, thus simultaneously op-
or HBr as an acid catalyst may react with the desired product HMF timizing catalytic activity and selectivity. Notably, water as a
to yield a more stable compound 5-chloromethylfurfural (CMF) or convenient dispersant for lignocellulosic materials [1115] can be
5-bromomethylfurfural (BMF) [1096,1097]. generated in situ by dehydration and hydrogenolysis, while it is likely
to cause poisoning of active sites [1116]. From the discussion above,
6.3. Control of functional materials solid functional catalysts with high water tolerance, adjusted surface
polarity, and tailored porosity can enhance eciency in transfor-
Apart from selecting suitable biomass pretreatment and reac- mations to a large degree. Paramagnetic and nano-sized materials
tion media, design of an optimal catalytic system including the type have also been suggested as methods in catalyst design, however
of reactor and heating, as well as catalyst itself is needed to achieve these materials are still in their infancy stage, regarding their uni-
the ecient and selective transformation of biomass into desired formity, recyclability and accessibility [11171119].
products [10981100]. From the preceding sections, it can be seen
that much emphasis has been placed on the preparation and ap- 6.4. Heating modes including microwave and ultrasound
plication of the multifunctional catalysts containing acid/base sites
and/or metal particles for biomass processing. After modication In past decades, valorization of biomass using conventional
with selected functional groups [11011103], the resulting multi- heating modes, especially pyrolysis, has been extensively investi-
functional catalytic materials have many possibilities for eciently gated. A wide range of feedstocks ranging from organic residues to
converting biomass through: biopolymers have been studied and simple scale-up for pyrolysis
H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194 173

is possible, while high energy consumption (T > 600 C) and low microalgae cells to promote oil release [1139]. With respect to the
quality products containing the formation of polycyclic aromatic hy- production of biodiesel from as-prepared oils with the assistance
drocarbons and CO2 are issues that require urgent attention [1120]. of base, acid and/or enzyme functionalized catalysts, ultrasound can
In this respect, microwave irradiation can offer appropriate process promote the mass transfer of immiscible reactants, thus shorten-
control by its instantaneous heating mode with rapid and conve- ing reaction time [1140,1141]. Nevertheless, ultrasound is less
nient start-up and shutdown, thus facilitating the adjustment of ecient for transesterication than magnetic stirring at a low
reaction parameters such as time, temperature and power for methanol/oil ratio of <7/1 and temperature of 65 C, but could tol-
biomass processing [1121,1122]. In microwave processes, both erate excess methanol (>7/1) through vaporizing some of methanol
thermal and non-thermal effects are often involved in processing caused by the effect of ultrasonic cavitation [1142]. Enzymatic hy-
of biomass. In the overall heating process, the rapid rise in tem- drolysis of lignocelluloses for bioethanol production can be
perature resulting from microwave irradiation causes the intensied with ultrasound [1143,1144], with biodiesel and
vaporization of intramolecular water contained in biomass, hence bioethanol being favorably produced from different fractions of
increasing the intra-particle pressure to loosen the structure of bio- biomass.
polymers by expansion [1123]. The destructive effect of ultrasound
causes generation of rapidly expanding and contracting water 7. Conclusions and future outlook
bubbles within the lignocellulosic units, leading to the compres-
sion and extension of the particles [1124]. Both microwave and Bifunctional catalytic materials have been demonstrated to have
ultrasound are promising auxiliaries for increasing the contact area outstanding potential in producing chemicals and biofuels e-
between solid bifunctional catalysts and lignocellulosic substrates ciently and with high selectivity through multi-step conversions of
and still need to be studied for many reaction systems [1125,1126]. biomass in one-pot processes. The role of basicity or Lewis acidity
Apart from biomass pretreatment using microwave or ultra- is mainly in sugar isomerization, as well as in upgrading of plat-
sound irradiation, the combination of hydrothermal conditions with form molecules through condensation and DielsAldol reactions.
microwave irradiation involving moderate temperatures of 100 Simultaneous addition or presence of strong Bronsted acid sites ac-
200 C has been demonstrated to be applicable to the transformation celerates the process of dehydration and oxygen removal. By
of many kinds of lignocellulosic biomass into molecules with a high introducing noble metals or transition metals into acid-initiated re-
degree of functionality [1127]. Xie et al. [1128] found that Ni/ actions, the oxygen removal capacity can be further enhanced
Al2O3 was effective for tar removal and for the fast microwave- through hydrolytic hydrogenation or hydrogenolysis, notably, de-
assisted gasication of corn stover at 900 C, in which syngas in a carboxylation reactions may occur at relatively high temperatures.
yield above 80% was produced. Little change in the structure of Ni/ On the contrary, some types of oxygenates can be produced from
Al2O3 catalyst was detected with XRD (X-ray diffraction) even after bio-based small molecules over basemetal dual-functional cata-
being reused for three times, indicating the good stability of the lysts, or directly from biomass derivatives promoted by acid
nickel based catalyst to resist the deactivation caused by coking or metal dual active sites. However, incompatibility issues associated
sintering. With the assistance of char as microwave absorber, rapid with competing reactions are often obstacles to increasing product
heat-up to high temperatures within seconds can be achieved in selectivity. For example, the catalytic production of hydrogenated
the pyrolysis of oil palm biomass (shell and bers) [1128]. In par- furanic compounds from mono-saccharides is likely to be realized
ticular, the yields and rapid heating of microwave pyrolysis products through cascade dehydrationhydrogenation. In fact, hexitols such
such as bio-oils, chars, and gases are closely dependent on the ratio as sorbitol and mannitol are generally formed as dominant prod-
of biomass substrate to microwave absorber [1129]. Furthermore, ucts through direct hydrogenation of sugars rather than HMF or
biomass in large particle sizes is able to be used directly in micro- furfural in-situ generated by water-removing processes. In this
wave heating, hence saving the cost of grinding and moisture regards, several points affecting biomass valorization may be taken
removal. into consideration for the establishment of well-dened catalytic
In the presence of activated carbon under the reaction condi- systems, associated with bifunctionality and relevant auxiliaries:
tions of temperature and retention time varied with a xed
microwave power input of 700 W, bio-oils with high concentra- (1) According to specic reactions, the rate of Bronsted/Lewis acid
tions of phenol (39%) and phenolics (67%) are obtained in the sites should be well adjusted so as to suppress the forma-
catalytic microwave pyrolysis of lignocellulosic biomass, while a high tion of humins or byproducts. Besides optimizing catalyst
concentration of esters (42%) is obtained in a formic acid/ethanol composition, the coverage of undesirable catalytic sites with
reaction medium using Zn powder as catalyst [1130]. It is appar- other chemical species in a bond-binding mode could be
ent that fossil fuel substitutes are likely to be generated from biomass applied as a technique in catalyst design.
pyrolysis assisted and enhanced with microwave irradiation [1131]. (2) The coexistence of acid and base sites can be realized by con-
In parallel, the microwave-assisted conversion of carbohydrates to currently immobilizing them into a solid material. However,
make a wide range of sugar-derivative scaffolds has been pro- the acid/base strength and content are limited with this ap-
posed [1132]. proach, owing to the possible neutralization caused by [H+]
In comparison to conventional oil bath heating mode (100 C, liberation or leaching. In this case, the choice of appropriate
10 h), microwave irradiation at a power of 400 W was able to sig- solvents is important to inhibit this phenomenon. Discrete
nicantly reduce the reaction time (8 min) with increased yields distribution of base and acid sites into different fractions (e.g.,
of reducing sugars (7% vs. 48%) in the hydrolysis of cellulose over core/shell) of a solid catalyst may be another way to address
a solid acid like HY(5) [1133]. To some extent, this microwave- this issue.
assisted catalytic system is capable of simplifying the downstream (3) The incompatibility of cascade reactions catalyzed by acid
processing. Related studies on the ecient and rapid production of metal bifunctional materials can be undoubtedly overcome
LA and furans (e.g., HMF and furfural) from simple sugars and even by controlling the pressure of H2/O2, hydrophilicity and hy-
lignocellulosic biomass with microwave well conrm the promo- drophobicity of catalysts, size/dispersion of metals, acid type/
tion effect of such the microwave heating mode [11341137]. Both strength, and reaction time/temperature. Therefore, the
microwave and ultrasound show enhanced activity on the direct reaction parameters must be considered with the most im-
transesterication of the as-harvested algae biomass [1138], which portant ones being applicable for selective transformation of
was illustrated to be realized by accelerating the disruption of the biomass via multiple catalytic processes.
174 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

(4) In general, basemetal dual-functional catalysts are highly [9] Li H, Bhadury PS, Riisager A, Yang S. One-pot transformation of
polysaccharides via multi-catalytic processes. Catal Sci Technol 2014;4:4138
active for oxidation reactions, but rarely employed for multi-
68.
catalytic processes. In view of their basicity, the coupling of [10] Guo N, Caratzoulas S, Doren DJ, Sandler SI, Vlachos DG. A perspective on the
biomass pretreatment with succedent hydrogenation should modeling of biomass processing. Energy Environ Sci 2012;5:670316.
nd many new applications. [11] Notestein JM, Katz A. Enhancing heterogeneous catalysis through cooperative
hybrid organicinorganic interfaces. Chem Eur J 2006;12:395465.
(5) Apart from organocatalysis, the valorization of biomass de- [12] Margelefsky EL, Zeidan RK, Davis ME. Cooperative catalysis by silica-supported
rivatives through chemoenzymatic and electrochemical organic functional groups. Chem Soc Rev 2008;37:111826.
catalysis has been developed in recent years. Within all of [13] Daz U, Brunelab D, Corma A. Catalysis using multifunctional organosiliceous
hybrid materials. Chem Soc Rev 2013;42:408397.
these catalytic systems, biomass pretreatment is a vital step [14] Climent MJ, Corma A, Iborra S, Sabater MJ. Heterogeneous catalysis for
to achieve high digestibility, productivity and practicality. It tandem reactions. ACS Catal 2014;4:87091.
can be expected that there will be an increase in use of [15] Mehdi H, Fbos V, Tuba R, Bodor A, Mika LT, Horvth IT. Integration of
homogeneous and heterogeneous catalytic processes for a multi-step
chemoenzymatic and electrochemical catalysis methods to conversion of biomass: from sucrose to levulinic acid, -valerolactone,
understand catalyst functionality as well as to develop unique 1,4-pentanediol, 2-methyl-tetrahydrofuran, and alkanes. Top Catal
transformation systems for biomass valorization. 2008;48:4954.
[16] Cai CM, Zhang T, Kumar R, Wyman CE. Integrated furfural production as a
(6) As to the general characteristics of catalysts, functionality in renewable fuel and chemical platform from lignocellulosic biomass. J Chem
aqueous systems, recoverability and dispersibility can be en- Technol Biotechnol 2014;89:210.
hanced by innovative material composites, such as the [17] Shibasaki M, Kanai M, Matsunaga S, Kumagai N. Recent progress in
asymmetric bifunctional catalysis using multimetallic systems. Acc Chem Res
introduction of paramagnetic cores and nano-sizing of the ma-
2009;42:111727.
terials. Improvements in catalyst uniformity, stability and [18] Allen AE, MacMillan DWC. Synergistic catalysis: a powerful synthetic strategy
recyclability are essential for bifunctional catalytic systems for new reaction development. Chem Sci 2012;3:63358.
to realize industrial practicality. [19] Wasilke JC, Obrey SJ, Baker RT, Bazan GC. Concurrent tandem catalysis. Chem
Rev 2005;105:100120.
(7) Although bifunctional catalysts still requires experimental [20] Lee JM, Na Y, Han H, Chang S. Cooperative multi-catalyst systems for one-pot
trials for their effective development, computational methods organic transformations. Chem Soc Rev 2004;33:30212.
(e.g., DFT and ab initio methods) can provide some guid- [21] Sheldon RA. Atom eciency and catalysis in organic synthesis. Pure Appl
Chem 2000;72:123346.
ance into the inclusion of catalytic sites and insight into [22] Manzer LE. Recent developments in the conversion of biomass to renewable
preferred congurations or site arrangements. fuels and chemicals. Top Catal 2010;53:11936.
[23] Luo L, van der Voet E, Huppes G. Biorening of lignocellulosic feedstock
Technical, economic and environmental considerations. Bioresour Technol
In conclusion, bifunctional catalytic materials have many ad- 2010;101:502332.
vantages over monofunctional catalysts in eciency and in simplicity [24] Deng W, Zhang Q, Wang Y. Polyoxometalates as ecient catalysts for
of operation. Bifunctional catalytic materials will play a vital role transformations of cellulose into platform chemicals. Dalton Trans
2012;41:981731.
in the development of ecient biorenery production systems al- [25] Agbor VB, Cicek N, Sparling R, Berlin A, Levin DB. Biomass pretreatment:
though their large-scale application will depend on catalyst stability, fundamentals toward application. Biotechnol Adv 2011;29:67585.
product selectivity, and possibly the use of creative auxiliaries such [26] Climent MJ, Corma A, Iborra S. Converting carbohydrates to bulk chemicals
and ne chemicals over heterogeneous catalysts. Green Chem 2011;13:520
as reactor design and heating modes. Many opportunities exist for
40.
developing bifunctional catalytic materials on both fundamental and [27] Li H, Zhang Q, Yang S. Catalytic cascade dehydration-etherication of fructose
applied levels. The numerous studies presented in this review serve into 5-ethoxymethylfurfural with SO3H-functionalized polymers. Int J Chem
as the foundation for realizing practical multi-catalytic processes Eng 2014;2014:17.
[28] Nakagawa Y, Tamura M, Tomishige K. Catalytic reduction of biomass-derived
with bifunctional catalytic materials. furanic compounds with hydrogen. ACS Catal 2013;3:265568.
[29] Siankevich S, Savoglidis G, Fei Z, Laurenczy G, Alexander DTL, Yan N, et al.
A novel platinum nanocatalyst for the oxidation of 5-hydroxymethylfurfural
Acknowledgments into 2,5-furandicarboxylic acid under mild conditions. J Catal 2014;315:67
74.
[30] Liguori F, Moreno-Marrodan C, Barbaro P. Environmentally friendly synthesis
This work was nancially supported by Nanjing Agricultural Uni- of -valerolactone by direct catalytic conversion of renewable sources. ACS
versity, the Chinese Academy of Sciences [135 program (XTBG- Catal 2015;5:188294.
T02) and equipment R&D grant (YZ201260)], Natural Science [31] James OO, Maity S, Usman LA, Ajanaku KO, Ajani OO, Siyanbola TO, et al.
Towards the conversion of carbohydrate biomass feedstocks to biofuels via
Foundation of China (21576059), and Yunnan Provincial Govern- hydroxylmethylfurfural. Energy Environ Sci 2010;3:183350.
ment (Hundreds of High-Level Overseas Talents). [32] Huang X, Kornyi TI, Boot MD, Hensen EJM. Catalytic depolymerization of
lignin in supercritical ethanol. ChemSusChem 2014;7:227688.
[33] Bahadar A, Khan MB. Progress in energy from microalgae: a review. Renew
References Sust Energy Rev 2013;27:12848.
[34] Lee SB, Jeong GT. Catalytic conversion of chitosan to 5-hydroxymethylfurfural
under low temperature hydrothermal process. Appl Biochem Biotechnol
[1] Kamm B, Gruber PR, Kamm M. Bioreneries-industrial processes and 2015;176:115161.
products: status quo and future directions. 1st ed. Weinheim: Wiley-VCH; [35] Borges ME, Daz L. Recent developments on heterogeneous catalysts for
2006. biodiesel production by oil esterication and transesterication reactions:
[2] Dusselier M, Mascal M, Sels BF. Top chemical opportunities from carbohydrate a review. Renew Sust Energy Rev 2012;16:283949.
biomass: a chemists view of the biorenery. Top Curr Chem 2014;353:140. [36] Tan HW, Abdul Aziz AR, Aroua MK. Glycerol production and its applications
[3] Yung MM, Jablonski WS, Magrini-Bair KA. Review of catalytic conditioning as a raw material: a review. Renew Sust Energy Rev 2013;27:11827.
of biomass-derived syngas. Energ Fuel 2009;23:187487. [37] Alonso DM, Bond JQ, Dumesic JA. Catalytic conversion of biomass to biofuels.
[4] Fang Z. Noncatalytic fast hydrolysis of wood. Bioresour Technol Green Chem 2010;12:1493513.
2011;102:358790. [38] Chatterjee C, Pong F, Sen A. Chemical conversion pathways for carbohydrates.
[5] Cheng YT, Jae J, Shi J, Fan W, Huber GW. Production of renewable aromatic Green Chem 2015;17:4071.
compounds by catalytic fast pyrolysis of lignocellulosic biomass with [39] Kobayashi H, Fukuoka A. Synthesis and utilisation of sugar compounds
bifunctional Ga/ZSM-5 catalysts. Angew Chem Int Ed 2012;51:138790. derived from lignocellulosic biomass. Green Chem 2013;15:174063.
[6] Baliban RC, Elia JA, Floudas CA. Biomass to liquid transportation fuels (BTL) [40] Montingelli ME, Tedesco S, Olabi AG. Biogas production from algal biomass:
systems: process synthesis and global optimization framework. Energ Environ a review. Renew Sust Energy Rev 2015;43:96172.
Sci 2013;6:26787. [41] Stcker M. Biofuels and biomass-to-liquid fuels in the biorenery: catalytic
[7] Zhang Q, Chang J, Wang T, Xu Y. Review of biomass pyrolysis oil properties conversion of lignocellulosic biomass using porous materials. Angew Chem
and upgrading research. Energy Conv Manage 2007;48:8792. Int Ed 2008;47:920011.
[8] Jin F, Enomoto H. Rapid and highly selective conversion of biomass into [42] Xavier NM, Lucas SD, Rauter AP. Zeolites as ecient catalysts for key
value-added products in hydrothermal conditions: chemistry of acid/base- transformations in carbohydrate chemistry. J Mol Catal A Chem
catalysed and oxidation reactions. Energy Environ Sci 2011;4:38297. 2009;305:849.
H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194 175

[43] Tekin K, Karagz S, Bekta S. A review of hydrothermal biomass processing. [73] Su Y, Brown HM, Huang X, Zhou X, Amonette JE, Zhang ZC. Single-step
Renew Sust Energy Rev 2014;40:67387. conversion of cellulose to 5-hydroxymethylfurfural (HMF), a versatile
[44] Morais ARC, Lopes AMDC, Bogel-ukasik R. Carbon dioxide in biomass platform chemical. Appl Catal A Gen 2009;361:11722.
processing: contributions to the green biorenery concept. Chem Rev [74] Binder JB, Raines RT. Simple chemical transformation of lignocellulosic
2015;115:327. biomass into furans for fuels and chemicals. J Am Chem Soc 2009;131:1979
[45] Spivey JJ, Egbebi A. Heterogeneous catalytic synthesis of ethanol from 85.
biomass-derived syngas. Chem Soc Rev 2007;36:151428. [75] Yi YB, Lee JW, Choi YH, Park SM, Chung CH. Simple process for production
[46] Lin YC, Huber GW. The critical role of heterogeneous catalysis in of hydroxymethylfurfural from raw biomasses of girasol and potato tubers.
lignocellulosic biomass conversion. Energy Environ Sci 2009;2:6880. Biomass Bioenergy 2012;39:4848.
[47] Sani YM, Dual WMAW, Aziz ARA. Activity of solid acid catalysts for biodiesel [76] Hu L, Sun Y, Lin L, Liu S. Catalytic conversion of glucose into
production: a critical review. Appl Catal A Gen 2014;470:14061. 5-hydroxymethylfurfural using double catalysts in ionic liquid. J Taiwan Inst
[48] Dutta S, De S, Saha B. Advances in biomass transformation to 5- Chem Eng 2012;43:71823.
hydroxymethylfurfural and mechanistic aspects. Biomass Bioenergy [77] Yang Y, Hu C, Abu-Omar MM. The effect of hydrochloric acid on the
2013;55:35569. conversion of glucose to 5-hydroxymethylfurfural in AlCl3H2O/THF biphasic
[49] Pham TN, Sooknoi T, Crossley SP, Resasco DE. Ketonization of carboxylic acids: medium. J Mol Catal A Chem 2013;376:98102.
mechanisms, catalysts, and implications for biomass conversion. ACS Catal [78] Pagn-Torres YJ, Wang T, Gallo JMR, Shanks BH, Dumesic JA. Production of
2013;3:245673. 5-hydroxymethylfurfural from glucose using a combination of Lewis and
[50] Williams PJB, Laurensa LML. Microalgae as biodiesel & biomass feedstocks: Bronsted acid catalysts in water in a biphasic reactor with an alkylphenol
review & analysis of the biochemistry, energetics & economics. Energy solvent. ACS Catal 2012;2:9304.
Environ Sci 2010;3:55490. [79] Tao F, Song H, Yang J, Chou L. Catalytic hydrolysis of cellulose into furans in
[51] Abbasi T, Abbasi SA. Biomass energy and the environmental impacts MnCl2-ionic liquid system. Carbohyd Polym 2011;85:3638.
associated with its production and utilization. Renew Sust Energy Rev [80] Zhang ZH, Wang Q, Xie HB, Liu WJ, Zhao ZB. Catalytic conversion of
2010;14:91937. carbohydrates into 5-hydroxymethylfurfural by germanium(IV) chloride in
[52] Delidovich I, Leonhard K, Palkovits R. Cellulose and hemicellulose valorisation: ionic liquids. ChemSusChem 2011;4:1318.
an integrated challenge of catalysis and reaction engineering. Energy Environ [81] Tao FR, Song HL, Chou LJ. Hydrolysis of cellulose by using catalytic amounts
Sci 2014;7:280330. of FeCl2 in ionic liquids. ChemSusChem 2010;3:1298303.
[53] Shimizu K, Satsuma A. Toward a rational control of solid acid catalysis for [82] Tao FT, Song HL, Chou LJ. Catalytic conversion of cellulose to chemicals in
green synthesis and biomass conversion. Energy Environ Sci 2011;4:3140 ionic liquid. Carbohydr Res 2011;346:5863.
53. [83] Zhou L, Liang R, Ma Z, Wu T, Wu Y. Conversion of cellulose to HMF in
[54] Hu L, Zhao G, Hao W, Tang X, Sun Y, Lin L, et al. Catalytic conversion of ionic liquid catalyzed by bifunctional ionic liquids. Bioresour Technol
biomass-derived carbohydrates into fuels and chemicals via furanic aldehydes. 2013;129:4505.
RSC Adv 2012;2:11184206. [84] Li H, Zhang Q, Liu X, Chang F, Hu D, Zhang Y, et al. InCl3-ionic liquid catalytic
[55] Simmie JM, Wrmel J. Harmonising production, properties and environmental system for ecient and selective conversion of cellulose into
consequences of liquid transport fuels from biomass2,5-Dimethylfuran as 5-hydroxymethylfurfural. RSC Adv 2013;3:364854.
a case study. ChemSusChem 2013;6:3641. [85] Wu L, Song J, Zhang B, Zhou B, Zhou H, Fan H, et al. Very ecient conversion
[56] Li H, Zhang Q, Bhadury PS, Yang S. Furan-type compounds from carbohydrates of glucose to 5-hydroxymethylfurfural in DBU-based ionic liquids with
via heterogeneous catalysis. Curr Org Chem 2014;18:54797. benzenesulfonate anion. Green Chem 2014;16:393541.
[57] Rosatella AA, Simeonov SP, Frade RFM, Carlos AMA. 5-Hydroxymethylfurfural [86] Hu Z, Liu B, Zhang Z, Chen L. Conversion of carbohydrates into
(HMF) as a building block platform: biological properties, synthesis and 5-hydroxymethylfurfural catalyzed by acidic ionic liquids in dimethyl
synthetic applications. Green Chem 2011;13:75493. sulfoxide. Ind Crops Prod 2013;50:2649.
[58] Gandini A. Furans as offspring of sugars and polysaccharides and progenitors [87] Liu DJ, Chen EYX. Polymeric ionic liquid (PIL)-supported recyclable catalysts
of a family of remarkable polymers: a review of recent progress. Polym Chem for biomass conversion into HMF. Biomass Bioenergy 2013;48:181
2010;1:24551. 90.
[59] Qian XH. Mechanisms and energetics for Bronsted acid-catalyzed glucose [88] Li H, Zhang Q, Liu X, Chang F, Zhang Y, Xue W, et al. Immobilizing Cr3+
condensation, dehydration and isomerization reactions. Top Catal with SO3H-functionalized solid polymeric ionic liquids as ecient and
2012;55:21826. reusable catalysts for selective transformation of carbohydrates into
[60] Qian XH. Mechanisms and energetics for acid catalyzed Beta-D-glucose 5-hydroxymethylfurfural. Bioresour Technol 2013;144:217.
conversion to 5-hydroxymethylfurfurl. J Phys Chem A 2011;115:117408. [89] Degirmenci V, Pidko EA, Magusin PCMM, Hensen EJM. Towards a selective
[61] Qian XH, Nimlos MR, Davis M, Johnson DK, Himmel ME. Ab initio molecular heterogeneous catalyst for glucose dehydration to 5-hydroxymethylfurfural
dynamics simulations of Beta-D-glucose and Beta-D-xylose degradation in water: CrCl 2 catalysis in a thin immobilized ionic liquid layer.
mechanisms in acidic aqueous solution. Carbohydr Res 2005;340:2319 ChemCatChem 2011;3:96972.
27. [90] Crisci AJ, Tucker MH, Dumesic JA, Scott SL. Bifunctional solid catalysts for
[62] Guan J, Cao Q, Guo X, Mu X. The mechanism of glucose conversion to the selective conversion of fructose to 5-hydroxymethylfurfural. Top Catal
5-hydroxymethylfurfural catalyzed by metal chlorides in ionic liquid: a 2010;53:118592.
theoretical study. Comp Theor Chem 2011;963:45362. [91] Liu H, Wang H, Li Y, Yang W, Song C, Li H, et al. Glucose dehydration to
[63] Pidko EA, Degirmenci V, Hensen EJM. On the mechanism of Lewis acid 5-hydroxymethylfurfural in ionic liquid over Cr3+-modied ion exchange resin.
catalyzed glucose transformations in ionic liquids. ChemCatChem RSC Adv 2015;5:92907.
2012;4:126371. [92] Lee YY, Wu KCW. Conversion and kinetics study of fructose-to-5-
[64] Bao Q, Qiao K, Tomida D, Yokoyama C. Preparation of 5-hydroymethylfurfural hydroxymethylfurfural (HMF) using sulfonic and ionic liquid groups bi-
by dehydration of fructose in the presence of acidic ionic liquid. Catal functionalized mesoporous silica nanoparticles as recyclable solid
Commun 2008;9:13838. catalysts in DMSO systems. Phys Chem Chem Phys 2012;14:13914
[65] van Dam HE, Kieboom APG, van Bekkum H. The conversion of fructose and 17.
glucose in acidic media: formation of hydroxymethylfurfural. Starch/Strke [93] Zhang Z, Zhao ZK. Production of 5-hydroxymethylfurfural from glucose
1986;38:95101. catalyzed by hydroxyapatite supported chromium chloride. Bioresour Technol
[66] Bao Q, Qiao K, Tomida D, Yokoyama C. 1-Methylimidazolium chlorosulfate 2011;102:39702.
([HMIm]SO3Cl): a novel ionic liquid with dual BronstedLewis acidity. Chem [94] Wang J, Ren J, Liu X, Xi J, Xia Q, Zu Y, et al. Direct conversion of carbohydrates
Lett 2010;39:7289. to 5-hydroxymethylfurfural using Sn-Mont catalyst. Green Chem
[67] Wrigstedt P, Keskivli J, Leskel M, Repo T. The role of salts and Bronsted 2012;14:250612.
acids in Lewis acid-catalyzed aqueous-phase glucose dehydration to [95] Zhang Y, Pan J, Gan M, Ou H, Yan Y, Shi W, et al. Acidchromic chloride
5-hydroxymethylfurfural. ChemCatChem 2015;7:5017. functionalized natural clay particles for enhanced conversion of one-pot
[68] Choudhary V, Mushrif SH, Ho C, Anderko A, Nikolakis V, Marinkovic NS, et al. cellulose to 5-hydroxymethylfurfural in ionic liquids. RSC Adv 2014;4:11664
Insights into the interplay of Lewis and Bronsted acid catalysts in glucose 72.
and fructose conversion to 5-(hydroxymethyl)furfural and levulinic acid in [96] Chareonlimkun A, Champreda V, Shotipruk A, Laosiripojana N. Reactions of
aqueous media. J Am Chem Soc 2013;135:39974006. C5 and C6-sugars, cellulose, and lignocellulose under hot compressed water
[69] van Putten RJ, van der Waal JC, de Jong E, Rasrendra CB, Heeres HJ, de Vries (HCW) in the presence of heterogeneous acid catalysts. Fuel 2010;89:2873
JG. Hydroxymethylfurfural, a versatile platform chemical made from 80.
renewable resources. Chem Rev 2013;113:1499597. [97] Joo JB, Vu A, Zhang Q, Dahl M, Gu M, Zaera F, et al. A sulfated ZrO2 hollow
[70] Zakrzewska ME, Bogel-Lukasik E, Bogel-Lukasik R. Ionic liquid mediated nanostructure as an acid catalyst in the dehydration of fructose to
formation of 5-hydroxymethylfurfural: a promising biomass derived building 5-hydroxymethylfurfural. ChemSusChem 2013;6:20018.
block. Chem Rev 2011;111:397417. [98] Dutta A, Patra AK, Dutta S, Saha B, Bhaumik A. Hierarchically porous
[71] Li H, Chang F, Zhang Y, Hu D, Jin L, Song B, et al. Recent progress titanium phosphate nanoparticles: an ecient solid acid catalyst for
towards transition metal-catalyzed direct conversion of cellulose to 5- microwave assisted conversion of biomass and carbohydrates into
hydroxymethylfurfural. Curr Catal 2012;1:22132. 5-hydroxymethylfurfural. J Mater Chem 2012;22:14094100.
[72] Zhao HB, Holladay JE, Brown H, Zhang ZC. Metal chlorides in ionic liquid [99] Kourieh R, Rakic V, Bennici S, Auroux A. Relation between surface acidity
solvents convert sugars to 5-hydroxymethylfurfural. Science 2007;316:1597 and reactivity in fructose conversion into 5-HMF using tungstated zirconia
600. catalysts. Catal Commun 2013;30:513.
176 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

[100] Li H, Zhang Q, Liu J, Liu X, Chang F, Liu Y, et al. Selective transformation of [125] Nikolla E, Romn-Leshkov Y, Moliner M, Davis ME. One-pot synthesis of
carbohydrates into HMF promoted by carboxylic acids modied ZrMo mixed 5-(hydroxymethyl)furfural from carbohydrates using tin-Beta zeolite. ACS
oxides. Biomass Conv Bioref 2014;4:5966. Catal 2011;1:40810.
[101] De S, Dutta S, Patra AK, Bhaumik A, Saha B. Self-assembly of mesoporous [126] Gallo JMR, Alonso DM, Mellmer MA, Dumesic JA. Production and upgrading
TiO2 nanospheres via aspartic acid templating pathway and its catalytic of 5-hydroxymethylfurfural using heterogeneous catalysts and biomass-
application for 5-hydroxymethyl-furfural synthesis. J Mater Chem derived solvents. Green Chem 2013;15:8590.
2011;21:1750510. [127] Crisci AJ, Tucker MH, Lee MY, Jang SG, Dumesic JA, Scott SL. Acid-
[102] Dutta S, De S, Patra AK, Sasidharan M, Bhaumik A, Saha B. Microwave assisted functionalized SBA-15-type silica catalysts for carbohydrate dehydration. ACS
rapid conversion of carbohydrates into 5-hydroxymethylfurfural catalyzed Catal 2011;1:71928.
by mesoporous TiO2 nanoparticles. Appl Catal A Gen 2011;409-10:133 [128] Li Y, Liu H, Song CH, Gu XM, Li HM, Zhu WS, et al. The dehydration of fructose
9. to 5-hydroxymethylfurfural eciently catalyzed by acidic ion-exchange resin
[103] Kuo IJ, Suzuki N, Yamauchi Y, Wu KCW. Cellulose-to-HMF conversion using in ionic liquid. Bioresour Technol 2013;133:34753.
crystalline mesoporous titania and zirconia nanocatalysts in ionic liquid [129] Gao H, Peng Y, Pan J, Zeng J, Song C, Zhang Y, et al. Synthesis and evaluation
systems. RSC Adv 2013;3:202834. of macroporous polymerized solid acid derived from pickering HIPEs for
[104] Atanda L, Mukundan S, Shrotri A, Ma Q, Beltramini J. Catalytic conversion catalyzing cellulose into 5-hydroxymethylfurfural in an ionic liquid. RSC Adv
of glucose to 5-hydroxymethyl-furfural with a phosphated TiO2 catalyst. 2014;4:4302938.
ChemCatChem 2015;7:78190. [130] Zhang Y, Pan J, Yan Y, Shi W, Yu L. Synthesis and evaluation of stable
[105] Armaroli T, Busca G, Carlini C, Giuttari M, Galletti AMR, Sbrana G. Acid sites polymeric solid acid based on halloysite nanotubes for conversion of one-pot
characterization of niobium phosphate catalysts and their activity in fructose cellulose to 5-hydroxymethylfurfural. RSC Adv 2014;4:23797806.
dehydration to 5-hydroxymethyl-2-furaldehyde. J Mol Catal A Chem [131] Wang J, Xu W, Ren J, Liu X, Lu G, Wang Y. Ecient catalytic conversion of
2000;151:23343. fructose into hydroxymethylfurfural by a novel carbon-based solid acid. Green
[106] Zhang Y, Wang J, Ren J, Liu X, Li X, Xia Y, et al. Mesoporous niobium Chem 2011;13:267881.
phosphate: an excellent solid acid for the dehydration of fructose to [132] Hu L, Zhao G, Tang X, Wu Z, Xu J, Lin L, et al. Catalytic conversion of
5-hydroxymethylfurfural in water. Catal Sci Technol 2012;2:248591. carbohydrates into 5-hydroxymethylfurfural over cellulose-derived
[107] Nakajima K, Baba Y, Noma R, Kitano M, Kondo JN, Hayashi S, et al. Nb2O5nH2O carbonaceous catalyst in ionic liquid. Bioresour Technol 2013;148:5017.
as a heterogeneous catalyst with water-tolerant Lewis acid sites. J Am Chem [133] Kuo CH, Poyraz AS, Jin L, Meng Y, Pahalagedara L, Chen SY, et al.
Soc 2011;133:42247. Heterogeneous acidic TiO2 nanoparticles for ecient conversion of biomass
[108] Yang F, Liu Q, Bai X, Du Y. Conversion of biomass into 5- derived carbohydrates. Green Chem 2014;16:78591.
hydroxymethylfurfural using solid acid catalyst. Bioresour Technol [134] Ordomsky VV, van der Schaaf J, Schouten JC, Nijhuis TA. Glucose dehydration
2011;102:34249. to 5-hydroxymethylfurfural in a biphasic system over solid acid foams.
[109] Jimnez-Morales I, Moreno-Recio M, Santamara-Gonzlez J, Maireles-Torres ChemSusChem 2013;6:1697707.
P, Jimnez-Lpez A. Mesoporous tantalum oxide as catalyst for dehydration [135] Chambon F, Rataboul F, Pinel C, Cabiac A, Guillon E, Essayem N. Cellulose
of glucose to 5-hydroxymethylfurfural. Appl Catal B: Environ 2014;154- hydrothermal conversion promoted by heterogeneous Bronsted and Lewis
5:1906. acids: remarkable eciency of solid Lewis acids to produce lactic acid. Appl
[110] Yang F, Liu Q, Yue M, Bai X, Du Y. Tantalum compounds as heterogeneous Catal B: Environ 2011;105:17181.
catalysts for saccharide dehydration to 5-hydroxymethylfurfural. Chem [136] Kourieh R, Bennici S, Marzo M, Gervasini A, Auroux A. Investigation of the
Commun 2011;47:446971. WO3/ZrO2 surface acidic properties for the aqueous hydrolysis of cellobiose.
[111] Jimnez-Morales I, Teckchandani-Ortiz A, Santamara-Gonzlez J, Catal Commun 2012;19:11926.
Maireles-Torres P, Jimnez-Lpez A. Selective dehydration of glucose to [137] Carlini C, Giuttari M, Galletti AMR, Sbrana G, Armaroli T, Busca G. Selective
5-hydroxymethylfurfural on acidicmesoporous tantalum phosphate. Appl saccharides dehydration to 5-hydroxymethyl-2-furaldehyde by heterogeneous
Catal B: Environ 2014;144:228. niobium catalysts. Appl Catal A Gen 1999;183:295302.
[112] Yamaguchi K, Sakurada T, Ogasawara Y, Mizuno N. Tin-tungsten mixed oxide [138] Carniti P, Gervasini A, Biella S, Auroux A. Niobic acid and niobium phosphate
as ecient heterogeneous catalyst for conversion of saccharides to furan as highly acidic viable catalysts in aqueous medium: fructose dehydration
derivatives. Chem Lett 2011;40:5423. reaction. Catal Today 2006;118:3738.
[113] Behera GC, Parida KM. One-pot synthesis of 5-hydroxymethylfurfural: a [139] Antal JMJ, Mok WSL. Mechanism of formation of 5-(hydroxymethyl)-2-
signicant biomass conversion over tin-promoted vanadium phosphate furaldehyde from D-fructose and sucrose. Carbohydr Res 1990;199:91109.
(SnVPO) catalyst. Catal Sci Technol 2013;3:327885. [140] Ordomsky VV, Sushkevich VL, Schouten JC, van der Schaaf J, Nijhuis TA.
[114] Daorattanachai P, Khemthong P, Viriya-empikul N, Laosiripojana N, Glucose dehydration to 5-hydroxymethylfurfural over phosphate catalysts.
Faungnawakij K. Conversion of fructose, glucose, and cellulose to J Catal 2013;300:3746.
5-hydroxymethylfurfural by alkaline earth phosphate catalysts in hot [141] Ogasawara Y, Uchida S, Yamaguchi K, Mizuno N. A tintungsten mixed oxide
compressed water. Carbohyd Res 2012;363:5861. as an ecient heterogeneous catalyst for CC bond-forming reactions. Chem
[115] Jimnez-Morales I, Santamara-Gonzlez J, Jimnez-Lpez A, Maireles-Torres Eur J 2009;15:43439.
P. Glucose dehydration to 5-hydroxymethylfurfural on zirconium containing [142] Jin X, Oishi T, Yamaguchi K, Mizuno N. Heterogeneously catalyzed ecient
mesoporous MCM-41 silica catalysts. Fuel 2014;118:26571. hydration of alkynes to ketones by tintungsten mixed oxides. Chem Eur J
[116] Jimnez-Morales I, Moreno-Recio M, Santamara-Gonzlez J, Maireles-Torres 2011;17:12617.
P, Jimnez-Lpez A. Production of 5-hydroxymethylfurfural from glucose [143] Ranoux A, Djanashvili K, Arends IWCE, Hanefeld U. B-TUD-1: a versatile
using aluminium doped MCM-41 silica as acid catalyst. Appl Catal B: Environ mesoporous catalyst. RSC Adv 2013;3:2152434.
2015;164:706. [144] Baba T, Watanabe H, Ono Y. Generation of acidic sites in metal salts of
[117] Fan C, Guan H, Zhang H, Wang J, Wang S, Wang X. Conversion of fructose heteropolyacids. J Phys Chem 1983;87:240611.
and glucose into 5-hydroxymethylfurfural catalyzed by a solid heteropolyacid [145] Shimizu K, Uozumi R, Satsuma A. Enhanced production of
salt. Biomass Bioenergy 2011;35:265965. hydroxymethylfurfural from fructose with solid acid catalysts by simple water
[118] Jadhav AH, Kim H, Hwang IT. An ecient and heterogeneous recyclable removal methods. Catal Commun 2009;10:184953.
silicotungstic acid with modied acid sites as a catalyst for conversion of [146] Qu Y, Huang C, Zhang J, Chen B. Ecient dehydration of fructose to
fructose and sucrose into 5-hydroymethylfurfural in superheated water. 5-hydroxymethylfurfural catalyzed by a recyclable sulfonated organic
Bioresour Technol 2013;132:34250. heteropolyacid salt. Bioresour Technol 2012;106:1702.
[119] Zhao Q, Wang L, Zhao S, Wang X, Wang S. High selective production of [147] Zhang Y, Degirmenci V, Li C, Hensen EJM. Phosphotungstic acid encapsulated
5-hydroymethylfurfural from fructose by a solid heteropolyacid catalyst. Fuel in metal-organic framework as catalysts for carbohydrate dehydration to
2011;90:228993. 5-hydroxymethylfurfural. ChemSusChem 2011;4:5964.
[120] Zhao S, Cheng M, Li J, Tian J, Wang X. One pot production of [148] Lanzafame P, Temi DM, Perathoner S, Spadaro AN, Centi G. Direct conversion
5-hydroxymethylfurfural with high yield from cellulose by a Bronsted-Lewis- of cellulose to glucose and valuable intermediates in mild reaction conditions
surfactant-combined heteropolyacid catalyst. Chem Commun 2011;47:2176 over solid acid catalysts. Catal Today 2012;179:17884.
8. [149] Taarning E, Osmundsen CM, Yang X, Voss B, Andersena SI, Christensen CH.
[121] Zheng H, Sun Z, Yi X, Wang S, Li J, Wang X, et al. A water-tolerant Zeolite-catalyzed biomass conversion to fuels and chemicals. Energy Environ
C16H3PW11CrO39 catalyst for the ecient conversion of monosaccharides into Sci 2011;4:793804.
5-hydroxymethylfurfural in a micellar system. RSC Adv 2013;3:23051 [150] Tan MX, Zhao L, Zhang Y. Production of 5-hydroxymethyl furfural from
6. cellulose in CrCl2/Zeolite/BMIMCl system. Biomass Bioenergy 2011;35:1367
[122] Otomo R, Yokoi T, Kondo JN, Tatsumi T. Dealuminated Beta zeolite as effective 70.
bifunctional catalyst for direct transformation of glucose to [151] Jadhav H, Taarning E, Pedersen CM, Bols M. Conversion of D-glucose
5-hydroxymethylfurfural. Appl Catal A Gen 2014;470:31826. into 5-hydroxymethylfurfural (HMF) using zeolite in [Bmim]Cl or
[123] Hu L, Wu Z, Xu J, Sun Y, Lin L, Liu S. Zeolite-promoted transformation of tetrabutylammonium chloride (TBAC)/CrCl2. Tetrahedron Lett 2012;53:983
glucose into 5-hydroxymethylfurfural in ionic liquid. Chem Eng J 5.
2014;244:13744. [152] Roman-Leshkov Y, Moliner M, Labinger JA, Davis ME. Mechanism of glucose
[124] Nandiwale KY, Galande ND, Thakur P, Sawant SD, Zambre VP, Bokade VV. isomerization using a solid Lewis acid catalyst in water. Angew Chem Int
One-pot synthesis of 5-hydroxymethylfurfural by cellulose hydrolysis over Ed 2010;49:89547.
highly active bimodal micro/mesoporous HZSM5 catalyst. ACS Sust Chem [153] Roy S, Bakhmutsky K, Mahmoud E, Lobo RF, Gorte RJ. Probing Lewis acid sites
Eng 2014;2:192832. in Sn-Beta zeolite. ACS Catal 2013;3:57380.
H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194 177

[154] Bermejo-Deval R, Orazov M, Gounder R, Hwang SJ, Davis ME. Active sites [182] Zhang L, Yu H, Wang P. Solid acids as catalysts for the conversion of D-xylose,
in Sn-Beta for glucose isomerization to fructose and epimerization to xylan and lignocellulosics into furfural in ionic liquid. Bioresour Technol
mannose. ACS Catal 2014;4:228897. 2013;136:51521.
[155] Lange JP, van der Heide E, van Buijtenen J, Price R. Furfural A promising [183] Bamueh HS, Alhamed YA, Daous MA. Furfural from midribs of date-palm
platform for lignocellulosic biofuels. ChemSusChem 2012;5:15066. trees by sulfuric acid hydrolysis. Ind Crops Prod 2013;42:4218.
[156] Aycock DF. Solvent applications of 2-methyltetrahydrofuran in organometallic [184] Agirrezabal-Telleria I, Larreategui A, Requies J, Gemez MB, Arias PL. Furfural
and biphasic reactions. Org Process Res Dev 2007;11:1569. production from xylose using sulfonic ion-exchange resins (Amberlyst) and
[157] Gurbuz EI, Wettstein SG, Dumesic JA. Conversion of hemicellulose to furfural simultaneous stripping with nitrogen. Bioresour Technol 2011;102:7478
and levulinic acid using biphasic reactors with alkylphenol solvents. 85.
ChemSusChem 2012;5:3837. [185] Dias AS, Pillinger M, Valente AA. Dehydration of xylose into furfural over
[158] Choudhary V, Pinar AB, Sandler SI, Vlachos DG, Lobo RF. Xylose isomerization micro-mesoporous sulfonic acid catalysts. J Catal 2005;229:41423.
to xylulose and its dehydration to furfural in aqueous media. ACS Catal [186] Lam E, Chong JH, Majid E, Liu Y, Hrapovic S, Leung ACW, et al. Carbocatalytic
2011;1:17248. dehydration of xylose to furfural in water. Carbon 2012;50:103343.
[159] Antal MJ Jr, Leesomboon T, Mok WS, Richards GN. Mechanism of formation [187] Hua D, Li PP, Wu Y, Chen Y, Yang M, Dang J, et al. Preparation of solid acid
of 2-furaldehyde from D-xylose. Carbohydr Res 1991;217:7185. catalyst packing AAO/SBA-15-SO3H and application for dehydration of xylose
[160] De Jong W, Marcotullio G. Overview of bioreneries based on co-production to furfural. J Ind Eng Chem 2013;19:13959.
of furfural, existing concepts and novel developments. Int J Chem React Eng [188] Agirrezabal-Telleria I, Requies J, Gemez MB, Arias PL. Dehydration of
2010;8:127. D-xylose to furfural using selective and hydrothermally stable arenesulfonic
[161] Choudhary V, Caratzoulas S, Vlachos DG. Insights into the isomerization of SBA-15 catalysts. Appl Catal B: Environ 2014;145:3442.
xylose to xylulose and lyxose by a Lewis acid catalyst. Carbohydr Res [189] Agirrezabal-Telleria I, Garca-Sancho C, Maireles-Torres P, Arias PL.
2013;368:8995. Dehydration of xylose to furfural using a Lewis or Brnsted acid catalyst and
[162] Choudhary V, Sandler SI, Vlachos DG. Conversion of xylose to furfural using N2 stripping. Chin J Catal 2013;34:14026.
Lewis and Bronsted acid catalysts in aqueous media. ACS Catal 2012;2:2022 [190] Liu QY, Yang F, Liu ZH, Li G. Preparation of SnO2Co3O4/C biochar catalyst
8. as a Lewis acid for corncob hydrolysis into furfural in water medium. J Ind
[163] Zhang J, Zhuang J, Lin L, Liu S, Zhang Z. Conversion of D-xylose into furfural Eng Chem 2015;26:4654.
with mesoporous molecular sieve MCM-41 as catalyst and butanol as the [191] Jehng JM, Wachs IE. The molecular structures and reactivity of supported
extraction phase. Biomass Bioenergy 2012;39:737. niobium oxide catalysts. Catal Today 1990;8:3755.
[164] Dias AS, Lima S, Brando P, Pillinger M, Rocha J, Valente AA. Liquid-phase [192] Sahu R, Dhepe PL. A one-pot method for the selective conversion of
dehydration of D-xylose over microporous and mesoporous niobium silicates. hemicellulose from crop waste into C5 sugars and furfural by using solid acid
Catal Lett 2006;108:17986. catalysts. ChemSusChem 2012;5:75161.
[165] Garca-Sancho C, Sdaba I, Moreno-Tost R, Mrida-Robles J, [193] Gallo JMR, Alonso DM, Mellmer MA, Yeap JH, Wong HC, Dumesic JA.
Santamara-Gonzlez J, Lpez-Granados M, et al. Dehydration of xylose to Production of furfural from lignocellulosic biomass using Beta zeolite and
furfural over MCM-41-supported niobium-oxide catalysts. ChemSusChem biomass-derived solvent. Top Catal 2013;56:177581.
2013;6:63542. [194] Lima S, Antunes MM, Fernandes A, Pillinger M, Ribeiro MF, Valente AA.
[166] Garca-Sancho C, Agirrezabal-Telleria I, Gemez MB, Maireles-Torres P. Acid-catalysed conversion of saccharides into furanic aldehydes in the
Dehydration of D-xylose to furfural using different supported niobia catalysts. presence of three-dimensional mesoporous Al-TUD-1. Molecules
Appl Catal B: Environ 2014;152-3:110. 2010;15:386377.
[167] Antunes MM, Lima S, Fernandes A, Pillinger M, Ribeiro MF, Valente AA. [195] Zanardi S, Alberti A, Cruciani G, Corma A, Forns V, Brunelli M. Crystal
Aqueous-phase dehydration of xylose to furfural in the presence of MCM-22 structure determination of zeolite Nu-6(2) and its layered precursor Nu-6(1).
and ITQ-2 solid acid catalysts. Appl Catal A Gen 2012;417-8:24352. Angew Chem Int Ed 2004;43:49337.
[168] Lima S, Antunes MM, Fernandes A, Pillinger M, Ribeiro MF, Valente AA. [196] Liu Y, Zhang W, Pinnavaia TJ. Steam-stable aluminosilicate mesostructures
Catalytic cyclodehydration of xylose to furfural in the presence of zeolite assembled from zeolite type Y seeds. J Am Chem Soc 2000;122:87912.
H-Beta and a micro/mesoporous Beta/TUD-1 composite material. Appl Catal [197] Dhepe PL, Sahua R. A solid-acid-based process for the conversion of
A Gen 2010;388:1418. hemicelluloses. Green Chem 2010;12:21536.
[169] Lima S, Pillinger M, Valente AA. Dehydration of D-xylose into furfural [198] Saha B, Mosier NS, Abu-Omar MM. Catalytic dehydration of lignocellulosic
catalysed by solid acids derived from the layered zeolite Nu-6(1). Catal derived xylose to furfural. Adv Plant Biol 2014;4:26776.
Commun 2008;9:21448. [199] Dias AS, Lima S, Pillinger M, Valente AA. Acidic cesium salts of 12-
[170] Grbz EI, Gallo JMR, Alonso DM, Wettstein SG, Lim WY, Dumesic JA. tungstophosphoric acid as catalysts for the dehydration of xylose into furfural.
Conversion of hemicellulose into furfural using solid acid catalysts in Carbohydr Res 2006;341:294653.
-valerolactone. Angew Chem Int Ed 2013;52:12704. [200] Werpy T, Petersen G. Top value added chemicals from biomass: vol. I results
[171] Lima S, Fernandes A, Antunes MM, Pillinger M, Ribeiro F, Valente AA. of screening for potential candidates from sugars and synthesis gas. Golden,
Dehydration of xylose into furfural in the presence of crystalline microporous CO: National Renewable Energy Lab; 2004.
silicoaluminophosphates. Catal Lett 2010;135:417. [201] Fernandes DR, Rocha AS, Mai EF, Mota CJA, Teixeira da Silva V. Levulinic acid
[172] Bhaumik P, Dhepe PL. Ecient, stable, and reusable silicoaluminophosphate esterication with ethanol to ethyl levulinate production over solid acid
for the one-pot production of furfural from hemicelluloses. ACS Catal catalysts. Appl Catal A Gen 2012;425-426:199204.
2013;3:2299303. [202] Kuwahara Y, Kaburagi W, Nemoto K, Fujitani T. Esterication of levulinic acid
[173] Dias AS, Lima S, Carriazo D, Rives V, Pillinger M, Valente AA. Exfoliated with ethanol over sulfated Si-doped ZrO2 solid acid catalyst: study of the
titanate, niobate and titanoniobate nanosheets as solid acid catalysts for the structureactivity relationships. Appl Catal A Gen 2014;476:18696.
liquid-phase dehydration of D-xylose into furfural. J Catal 2006;244:2307. [203] Hayes DJ. An examination of biorening processes, catalysis and challenges.
[174] Chareonlimkun A, Champreda V, Shotipruk A, Laosiripojana N. Catalytic Catal Today 2009;145:13851.
conversion of sugarcane bagasse, rice husk and corncob in the presence of [204] Lee A, Chaibakhsh N, Rahman MBA, Basri M, Tejo BA. Optimized enzymatic
TiO2, ZrO2 and mixed-oxide TiO2ZrO2 under hot compressed water (HCW) synthesis of levulinate ester in solvent-free system. Ind Crops Prod
condition. Bioresour Technol 2010;101:417986. 2010;32:24651.
[175] Dias AS, Lima S, Pillinger M, Valente AA. Modied versions of sulfated zirconia [205] Joshi H, Moser BR, Toler J, Smith WF, Walker T. Ethyl levulinate: a potential
as catalysts for the conversion of xylose to furfural. Catal Lett 2007;114:151 bio-based diluent for biodiesel which improves cold ow properties. Biomass
60. Bioenergy 2011;35:32626.
[176] Li H, Deng A, Ren J, Liu C, Lu Q, Zhong L, et al. Catalytic hydrothermal [206] Windom BC, Lovestead TM, Mascal M, Nikitin EB, Bruno TJ. Advanced
pretreatment of corncob into xylose and furfural via solid acid catalyst. distillation curve analysis on ethyl levulinate as a diesel fuel oxygenate and
Bioresour Technol 2014;158:31320. a hybrid biodiesel fuel. Energy Fuels 2011;25:187890.
[177] Antunes MM, Lima S, Fernandes A, Candeias J, Pillinger M, Rocha SM, et al. [207] Olson ES, Kjelden MR, Schlag AJ, Sharma RK. Chemicals and materials from
Catalytic dehydration of D-xylose to 2-furfuraldehyde in the presence of renewable resources. ACS Symp Ser 2001;784:5163.
Zr-(W,Al) mixed oxides. Tracing by-products using two-dimensional [208] Amarasekara AS, Wiredu B. Acidic ionic liquid catalyzed one-pot conversion
gas chromatography-time-of-ight mass spectrometry. Catal Today of cellulose to ethyl levulinate and levulinic acid in ethanol-water solvent
2012;195:12735. system. Bioenerg Res 2014;7:123743.
[178] Sdaba I, Lima S, Valente AA, Granados ML. Catalytic dehydration of xylose [209] Sun Z, Cheng M, Li H, Shi T, Yuan M, Wang X, et al. One-pot depolymerization
to furfural: vanadyl pyrophosphate as source of active soluble species. of cellulose into glucose and levulinic acid by heteropolyacid ionic liquid
Carbohydr Res 2011;346:278591. catalysis. RSC Adv 2012;2:905865.
[179] Shi X, Wu Y, Li P, Yi H, Yang M, Wang G. Catalytic conversion of xylose to [210] Zuo Y, Zhang Y, Fu Y. Catalytic conversion of cellulose into levulinic acid by
furfural over the solid acid SO42/ZrO2Al2O3/SBA-15 catalysts. Carbohydr Res a sulfonated chloromethyl polystyrene solid acid catalyst. ChemCatChem
2011;346:4807. 2014;6:7537.
[180] Agirrezabal-Telleria I, Hemmann F, Jger C, Arias PL, Kemnitz E. Functionalized [211] Saravanamurugan S, Riisager A. Solid acid catalysed formation of ethyl
partially hydroxylated MgF2 as catalysts for the dehydration of D-xylose to levulinate and ethyl glucopyranoside from mono- and disaccharides. Catal
furfural. J Catal 2013;305:8191. Commun 2012;17:715.
[181] Weingarten R, Tompsett GA, Conner WC Jr, Huber GW. Design of solid acid [212] Yang F, Fu J, Mo J, Lu X. Synergy of Lewis and Bronsted acids on catalytic
catalysts for aqueous-phase dehydration of carbohydrates: the role of Lewis hydrothermal decomposition of hexose to levulinic acid. Energy Fuels
and Bronsted acid sites. J Catal 2011;279:17482. 2013;27:69738.
178 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

[213] Saravanamurugan S, Riisager A. Zeolite catalyzed transformation of [245] Zhang Z-X, Bai P, Xu B, Yan ZF. Synthesis of mesoporous alumina TUD-1 with
carbohydrates to alkyl levulinates. ChemCatChem 2013;5:17547. high thermostability. J Porous Mat 2006;13:24550.
[214] Yaaini N, Amin NAS, Endud S. Characterization and performance of hybrid [246] Waller P, Shan Z, Marchese L, Tartaglione G, Zhou W, Jansen JC, et al. Zeolite
catalysts for levulinic acid production from glucose. Micropor Mesopor Mat nanocrystals inside mesoporous TUD-1: a high-performance catalytic
2013;171:1423. composite. Chem Eur J 2004;10:49706.
[215] Ramli NAS, ANAS. Fe/HY zeolite as an effective catalyst for levulinic acid [247] Maheshwari S, Jordan E, Kumar S, Bates FS, Penn RL, Shantz DF, et al. Layer
production from glucose: characterization and catalytic performance. Appl structure preservation during swelling, pillaring, and exfoliation of a zeolite
Catal B: Environ 2015;163:48798. precursor. J Am Chem Soc 2008;130:150716.
[216] Ramli NAS, Amin NAS. Catalytic hydrolysis of cellulose and oil palm biomass [248] Corma A, Forns V, Pergher SB, Bouglas JG, Maesen TLM. Delaminated zeolite
in ionic liquid to reducing sugar for levulinic acid production. Fuel Process precursors as selective acidic catalysts. Nature 1998;396:3536.
Technol 2014;128:4908. [249] Hamoudi S, Kaliaguine S. Sulfonic acid-functionalized periodic mesoporous
[217] Neves P, Lima S, Pillinger M, Rocha SM, Rocha J, Valente AA. Conversion of organosilica. Micropor Mesopor Mat 2003;59:195204.
furfuryl alcohol to ethyl levulinate using porous aluminosilicate acid catalysts. [250] Weingarten R, Kim YT, Tompsett GA, Fernndez A, Han KS, Hagaman EW,
Catal Today 2013;218-9:7684. et al. Conversion of glucose into levulinic acid with solid metal(IV) phosphate
[218] Suacharoen S, Tungasmita DN. Hydrothermolysis of carbohydrates to levulinic catalysts. J Catal 2013;304:12334.
acid using metal supported on porous aluminosilicate. J Chem Technol [251] Chen B, Li F, Huang Z, Lu T, Yuan Y, Yuan G. Integrated catalytic process to
Biotechnol 2013;88:153844. directly convert furfural to levulinate ester with high selectivity.
[219] Yang H, Wang L, Jia L, Qiu C, Pang Q, Pan X. Selective decomposition of ChemSusChem 2014;7:2029.
cellulose into glucose and levulinic acid over Fe-resin catalyst in NaCl solution [252] Yang G, Pidko EA, Hensen EJM. Mechanism of Bronsted acid-catalyzed
under hydrothermal conditions. Ind Eng Chem Res 2014;53:65628. conversion of carbohydrates. J Catal 2012;295:12232.
[220] Upare PP, Yoon JW, Kim MY, Kang HY, Hwang DW, Hwang YK, et al. Chemical [253] Pileidis FD, Titirici MM. Levulinic acid bioreneries: new challenges for
conversion of biomass-derived hexose sugars to levulinic acid over sulfonic ecient utilization of biomass. ChemSusChem 2016;9:56282.
acid-functionalized graphene oxide catalysts. Green Chem 2013;15:293543. [254] Carlson TR, Jae J, Lin YC, Tompsett GA, Huber GW. Catalytic fast pyrolysis of
[221] Peng L, Lin L, Zhang J, Shi J, Liu S. Solid acid catalyzed glucose conversion glucose with HZSM-5: the combined homogeneous and heterogeneous
to ethyl levulinate. Appl Catal A Gen 2011;397:25965. reactions. J Catal 2010;270:11024.
[222] Peng L, Lin L, Li H, Yang Q. Conversion of carbohydrates biomass into [255] Vispute TP, Zhang H, Sanna A, Xiao R, Huber GW. Renewable chemical
levulinate esters using heterogeneous catalysts. Appl Energy 2011;88:45906. commodity feedstocks from integrated catalytic processing of pyrolysis oils.
[223] Morales G, Osatiashtiani A, Hernndez B, Iglesias J, Melero JA, Paniagua M, Science 2010;330:12227.
et al. Conformal sulfated zirconia monolayer catalysts for the one-pot [256] Carlson TR, Jae J, Huber GW. Mechanistic insights from isotopic studies of
synthesis of ethyl levulinate from glucose. Chem Commun 2014;50:117425. glucose conversion to aromatics over ZSM-5. ChemCatChem 2009;1:107
[224] Chen H, Yu B, Jin S. Production of levulinic acid from steam exploded rice 10.
straw via solid superacid, S2O82/ZrO2SiO2Sm2O3. Bioresour Technol [257] Carlson TR, Vispute TP, Huber GW. Green gasoline by catalytic fast pyrolysis
2011;102:356870. of solid biomass derived compounds. ChemSusChem 2008;1:397400.
[225] Joshi SS, Zodge AD, Pandare KV, Kulkarni BD. Ecient conversion of cellulose [258] Carlson TR, Tompsett GA, Conner WC, Huber GW. Aromatic production
to levulinic acid by hydrothermal treatment using zirconium dioxide as a from catalytic fast pyrolysis of biomass-derived feedstocks. Top Catal
recyclable solid acid catalyst. Ind Eng Chem Res 2014;53:18796805. 2009;52:24152.
[226] Li K, Bai L, Amaniampong PN, Jia X, Lee JM, Yang Y. One-pot transformation [259] Mukarakate C, Watson MJ, ten Dam J, Baucherel X, Budhi S, Yung MM, et al.
of cellobiose to formic acid and levulinic acid over ionic-liquid-based Upgrading biomass pyrolysis vapors over -zeolites: role of silica-to-alumina
polyoxometalate hybrids. ChemSusChem 2014;7:26707. ratio. Green Chem 2014;16:4891905.
[227] Lin H, Strull J, Liu Y, Karmiol Z, Plank K, Miller G, et al. High yield production [260] Adjaye JD, Bakhshi NN. Production of hydrocarbons by catalytic upgrading
of levulinic acid by catalytic partial oxidation of cellulose in aqueous media. of a fast pyrolysis bio-oil. Part II: comparative catalyst performance and
Energy Environ Sci 2012;5:97737. reaction pathways. Fuel Process Technol 1995;45:185202.
[228] Peng L, Lin L, Li H. Extremely low sulfuric acid catalyst system for synthesis [261] Adjaye D, Bakhshi NN. Production of hydrocarbons by catalytic upgrading
of methyl levulinate from glucose. Ind Crops Prod 2012;40:13644. of a fast pyrolysis bio-oil. Part I: conversion over various catalysts. Fuel Process
[229] Yaaini N, Amin NAS, Asmadi M. Optimization of levulinic acid from Technol 1995;45:16183.
lignocellulosic biomass using a new hybrid catalyst. Bioresour Technol [262] Biscardi JA, Meitzner GD, Iglesia E. Structure and density of active Zn species
2012;116:5865. in Zn/H-ZSM5 propane aromatization catalysts. J Catal 1998;179:192202.
[230] Kruger JS, Choudhary V, Nikolakis V, Vlachos DG. Elucidating the roles of [263] Biscardi JA, Iglesia E. Reaction pathways and rate-determining steps in
zeolite HBEA in aqueous-phase fructose dehydration and hmf rehydration. reactions of alkanes on H-ZSM5 and Zn/H-ZSM5 catalysts. J Catal
ACS Catal 2013;3:127991. 1998;182:11728.
[231] Hegner J, Pereira KC, DeBoef B, Lucht BL. Conversion of cellulose to glucose [264] Fanchiang WL, Lin YC. Catalytic fast pyrolysis of furfural over H-ZSM-5 and
and levulinic acid via solid-supported acid catalysis. Tetrahedron Lett Zn/H-ZSM-5 catalysts. Appl Catal A Gen 2012;419-20:10210.
2010;51:23568. [265] Cheng YT, Jae J, Shi J, Fan W, Huber GW. Production of renewable aromatic
[232] Saravanamurugan S, Paniagua M, Melero JA, Riisager A. Ecient isomerization compounds by catalytic fast pyrolysis of lignocellulosic biomass with
of glucose to fructose over zeolites in consecutive reactions in alcohol and bifunctional Ga/ZSM-5 catalysts. Angew Chem 2012;124:141619.
aqueous media. J Am Chem Soc 2013;135:52469. [266] Jae J, Tompsett GA, Foster AJ, Hammond KD, Auerbach SM, Lobo RF, et al.
[233] Perego C, Bosetti A. Biomass to fuels: the role of zeolite and mesoporous Investigation into the shape selectivity of zeolite catalysts for biomass
materials. Micropor Mesopor Mat 2011;144:2839. conversion. J Catal 2011;279:25768.
[234] Moliner M, Roman-Leshkov Y, Davis ME. Tin-containing zeolites are highly [267] Li J, Li X, Zhou G, Wang W, Wang C, Komarneni S, et al. Catalytic fast pyrolysis
active catalysts for the isomerization of glucose in water. Proc Natl Acad Sci of biomass with mesoporous ZSM-5 zeolites prepared by desilication with
USA 2010;107:61648. NaOH solutions. Appl Catal A Gen 2011;470:11522.
[235] Gunther WR, Wang Y, Ji Y, Michaelis VK, Hunt ST, Grin RG, et al. Sn-Beta [268] Shao S, Zhang H, Heng L, Luo M, Xiao R, Shen D. Catalytic conversion of
zeolites with borate salts catalyse the epimerization of carbohydrates via biomass derivates over acid dealuminated ZSM-5. Ind Eng Chem Res
an intramolecular carbon shift. Nat Commun 2012;3:110916. 2014;53:158718.
[236] Chang CC, Wang Z, Dornath P, Cho HJ, Fan W. Rapid synthesis of Sn-Beta [269] Foster AJ, Jae J, Cheng Y-T, Huber GW, Lobo RF. Optimizing the aromatic yield
for the isomerization of cellulosic sugars. RSC Adv 2012;2:104757. and distribution from catalytic fast pyrolysis of biomass over ZSM-5. Appl
[237] Dapsens PY, Mondelli C, Prez-Ramrez J. Design of Lewis-acid centres in Catal A Gen 2012;423-4:15461.
zeolitic matrices for the conversion of renewable. Chem Soc Rev [270] Mayes HB, Nolte MW, Beckham GT, Shanks BH, Broadbelt LJ. The alphabet(a)
2015;44:702543. of glucose pyrolysis: computational and experimental investigations of
[238] Taarning E, Saravanamurugan S, Holm MS, Xiong JM, West RM, Christensen 5-hydroxymethylfurfural and levoglucosan formation reveal implications for
CH. Zeolite-catalyzed isomerization of triose sugars. ChemSusChem cellulose pyrolysis. ACS Sust Chem Eng 2014;2:146173.
2009;2:6257. [271] Torri C, Lesci IG, Fabbri D. Analytical study on the pyrolytic behaviour of
[239] Wang K, Xing Z, Ma Y, Wang Q. One-step preparation of N-tosylimines using cellulose in the presence of MCM-41 mesoporous materials. J Anal Appl
zeolite catalysts. Catal Lett 2008;123:12934. Pyrolysis 2009;85:1926.
[240] Peng L, Lin L, Zhang J, Zhuang J, Zhang B, Gong Y. Catalytic conversion of [272] Leng S, Wang X, Cai Q, Ma F, Liu Y, Wang J. Selective production of chemicals
cellulose to levulinic acid by metal chlorides. Molecules 2010;15:525872. from biomass pyrolysis over metal chlorides supported on zeolite. Bioresour
[241] Lourvanij K, Rorrer GL. Reactions of aqueous glucose solutions over solid-acid Technol 2013;149:3415.
Y-zeolite catalyst at 110-160 C. Ind Eng Chem Res 1993;32:1119. [273] Zhang H, Liu X, Lu M, Hu X, Lu L, Tian X, et al. Role of Bronsted acid in selective
[242] Cao X, Peng X, Sun S, Zhong L, Chen W, Wang S, et al. Hydrothermal production of furfural in biomass pyrolysis. Bioresour Technol 2014;169:800
conversion of xylose, glucose, and cellulose under the catalysis of transition 3.
metal sulfates. Carbohyd Polym 2015;118:4451. [274] Gayubo AG, Aguayo AT, Atutxa A, Valle B, Bilbao J. Undesired components
[243] Anand R, Maheswari R, Hanefeld U. Catalytic properties of the novel in the transformation of biomass pyrolysis oil into hydrocarbons on an
mesoporous aluminosilicate AlTUD-1. J Catal 2006;242:8291. HZSM-5 zeolite catalyst. J Chem Technol Biotechnol 2005;80:124451.
[244] Telalovic S, Ramanathan A, Mul G, Hanefeld U. TUD-1: synthesis and [275] Cheng YT, Huber GW. Chemistry of furan conversion into aromatics and
application of a versatile catalyst, carrier, material. J Mater Chem olens over HZSM-5: a model biomass conversion reaction. ACS Catal
2010;20:64258. 2011;1:61128.
H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194 179

[276] Shiramizu M, Toste FD. On the DielsAlder approach to solely biomass- lactic acid with bifunctional carbonsilica catalysts. J Am Chem Soc
derived polyethylene terephthalate (PET): conversion of 2,5-dimethylfuran 2012;134:10089101.
and acrolein into p-xylene. Chem Eur J 2011;17:124527. [305] Hayashi Y, Sasaki Y. Tin-catalyzed conversion of trioses to alkyl lactates in
[277] Vaitheeswaran S, Green SK, Dauenhauer P, Auerbach SM. On the way to alcohol solution. Chem Commun 2005;271618.
biofuels from furan: discriminating DielsAlder and ring-opening [306] West RM, Holm MS, Saravanamurugan S, Xiong J, Beversdorf Z, Taarning E,
mechanisms. ACS Catal 2013;3:201219. et al. Zeolite H-USY for the production of lactic acid and methyl lactate from
[278] Williams CL, Chang CC, Do P, Nikbin N, Caratzoulas S, Vlachos DG, et al. C3-sugars. J Catal 2010;269:12230.
Cycloaddition of biomass-derived furans for catalytic production of renewable [307] Wang JC, Masui Y, Onaka M. Conversion of triose sugars with alcohols to alkyl
p-xylene. ACS Catal 2012;2:9359. lactates catalyzed by Bronsted acid tin ion-exchanged montmorillonite. Appl
[279] Nikbin N, Do PT, Caratzoulas S, Lobo RF, Dauenhauer PJ, Vlachos DG. A DFT Catal B: Environ 2011;107:1359.
study of the acid-catalyzed conversion of 2,5-dimethylfuran and ethylene [308] Rasrendra CB, Fachri BA, Gusti I, Makertihartha BN, Adisasmito S, Heeres HJ.
to p-xylene. J Catal 2013;297:3543. Catalytic conversion of dihydroxyacetone to lactic acid using metal salts in
[280] Wang D, Osmundsen CM, Taarning E, Dumesic JA. Selective production of water. ChemSusChem 2011;4:76877.
aromatics from alkylfurans over solid acid catalysts. ChemCatChem [309] Assary RS, Curtiss LA. Theoretical study of 1,2-hydride shift associated with
2013;5:204450. the isomerization of glyceraldehyde to dihydroxy acetone by Lewis acid active
[281] Nikbin N, Feng S, Caratzoulas S, Vlachos DG. p-Xylene formation by site models. J Phys Chem A 2011;115:875460.
dehydrative aromatization of a DielsAlder product in Lewis and Bronsted [310] Pescarmona PP, Janssen KPF, Delaet C, Stroobants C, Houthoofd K, Philippaerts
acidic zeolites. J Phys Chem C 2014;118:2441524. A, et al. Zeolite-catalysed conversion of C 3 sugars to alkyl lactates. Green
[282] Chang C-C, Green SK, Williams CL, Dauenhauer PJ, Fan W. Ultra-selective Chem 2010;12:10839.
cycloaddition of dimethylfuran for renewable p-xylene with H-BEA. Green [311] Li L, Stroobants C, Lin K, Jacobs PA, Sels BF, Pescarmona PP. Selective
Chem 2014;16:5858. conversion of trioses to lactates over Lewis acid heterogeneous catalysts.
[283] Pacheco JJ, Davis ME. Synthesis of terephthalic acid via Diels-Alder reactions Green Chem 2011;13:117581.
with ethylene and oxidized variants of 5-hydroxymethylfurfural. Proc Natl [312] Liu J, Li H, Liu YC, Lu YM, He J, Liu XF, et al. Catalytic conversion of glucose
Acad Sci USA 2014;111:83637. to 5-hydroxymethylfurfural over nano-sized mesoporous Al2O3B2O3 solid
[284] Norton JA. The Diels-Alder diene synthesis. Chem Rev 1942;31:319523. acids. Catal Commun 2015;62:1923.
[285] Karger MH, Mazur Y. Mixed sulfonic-carboxylic anhydrides. II. Reactions with [313] Li H, Ren J, Zhong L, Sun R, Liang L. Production of furfural from xylose,
aliphatic ethers and amines. J Org Chem 1971;36:53240. water-insoluble hemicelluloses and water-soluble fraction of corncob via a
[286] Mahmoud E, Watson DA, Lobo RF. Renewable production of phthalic tin-loaded montmorillonite solid acid catalyst. Bioresour Technol
anhydride from biomass-derived furan and maleic anhydride. Green Chem 2015;176:2428.
2014;16:16775. [314] Schwiderski M, Kruse A, Grandl R, Dockendorf D. Comparison of the inuence
[287] Viil I, Bredihhin A, Meorg U, Vares L. Preparation of potential biofuel of a Lewis acid AlCl3 and a Bronsted acid HCl on the organosolv pulping of
5-ethoxymethylfurfural and other 5-alkoxymethylfurfurals in the presence beech wood. Green Chem 2014;16:156978.
of oil shale ash. RSC Adv 2014;4:568993. [315] Rai N, Caratzoulas S, Vlachos DG. Role of silanol group in Sn-Beta zeolite for
[288] Lanzafame P, Temi DM, Perathoner S, Centi G, Macario A, Aloise A, et al. glucose isomerization and epimerization reactions. ACS Catal 2013;3:2294
Etherication of 5-hydroxymethyl-2-furfural (HMF) with ethanol to biodiesel 8.
components using mesoporous solid acidic catalysts. Catal Today [316] Li G, Pidko EA, Hensen EJM. Synergy between Lewis acid sites and hydroxyl
2011;175:43541. groups for the isomerization of glucose to fructose over Sn-containing
[289] Kraus GA, Guney T. A direct synthesis of 5-alkoxymethylfurfural ethers from zeolites: a theoretical perspective. Catal Sci Technol 2014;4:224150.
fructose via sulfonic acid-functionalized ionic liquids. Green Chem [317] Zhang S, Jin F, Hu J, Huo Z. Improvement of lactic acid production from
2012;14:15936. cellulose with the addition of Zn/Ni/C under alkaline hydrothermal
[290] Bing L, Zhang Z, Deng K. Ecient one-pot synthesis of 5- conditions. Bioresour Technol 2011;102:19982003.
(ethoxymethyl)furfural from fructose catalyzed by a novel solid catalyst. Ind [318] Dijkmans J, Dusselier M, Gabrils D, Houthoofd K, Magusin PCMM, Huang
Eng Chem Res 2012;51:153316. S, et al. Cooperative catalysis for multistep biomass conversion with Sn/Al
[291] Balakrishnan M, Sacia ER, Bell AT. Etherication and reductive etherication Beta zeolite. ACS Catal 2015;5:92840.
of 5-(hydroxymethyl)furfural: 5-(alkoxymethyl)furfurals and 2,5- [319] Takagaki A, Jung JC, Hayashi S. Solid Lewis acidity of boehmite -AlO(OH)
bis(alkoxymethyl)furans as potential bio-diesel candidates. Green Chem and its catalytic activity for transformation of sugars in water. RSC Adv
2012;14:162634. 2014;4:4378591.
[292] Yang Y, Abu-Omar MM, Hu C. Heteropolyacid catalyzed conversion of [320] Jimnez-Morales I, Santamara-Gonzlez J, Maireles-Torres P, Jimnez-Lpez
fructose, sucrose, and inulin to 5-ethoxymethylfurfural, a liquid biofuel A. Mesoporous tantalum phosphate as acidic catalyst for the methanolysis
candidate. Appl Energy 2012;99:804. of sunower oil. Appl Catal B: Environ 2012;123-4:31623.
[293] Alam MI, De S, Dutta S, Saha B. Solid-acid and ionic-liquid catalyzed one-pot [321] Lee AF, Bennett JA, Manayil JC, Wilson K. Heterogeneous catalysis for
transformation of biorenewable substrates into a platform chemical and a sustainable biodiesel production via esterication and transesterication.
promising biofuel. RSC Adv 2012;2:68906. Chem Soc Rev 2014;43:7887916.
[294] Ren Y, Liu B, Zhang Z, Lin J. Silver-exchanged heteropolyacid catalyst [322] Di Serio M, Tesser R, Dimiccoli M, Cammarota F, Nastasi M, Santacesaria E.
(Ag 1 H 2 PW): an ecient heterogeneous catalyst for the synthesis of Synthesis of biodiesel via homogeneous Lewis acid catalyst. J Mol Catal A
5-ethoxymethylfurfural from 5-hydroxymethylfurfural and fructose. J Ind Eng Chem 2005;239:11115.
Chem 2015;21:112731. [323] Kulkarni MG, Gopinath R, Meher LC, Dalai AK. Solid acid catalyzed biodiesel
[295] Jia X, Ma J, Che P, Lu F, Miao H, Gao J, et al. Direct conversion of fructose-based production by simultaneous esterication and transesterication. Green Chem
carbohydrates to 5-ethoxymethylfurfural catalyzed by AlCl36H2O/BF3(Et)2O 2006;8:105662.
in ethanol. J Energy Chem 2013;22:937. [324] Shi W, Zhao J, Yuan X, Wang S, Wang X, Huo M. Effects of Bronsted and Lewis
[296] Lew CM, Rajabbeigi N, Tsapatsis M. One-pot synthesis of 5- acidities on catalytic activity of heteropolyacids in transesterication and
(ethoxymethyl)furfural from glucose using Sn-BEA and amberlyst catalysts. esterication reactions. Chem Eng Technol 2012;35:34752.
Ind Eng Chem Res 2012;51:53646. [325] Zhang L, Cui Y, Zhang C, Wang L, Wan H, Guan G. Biodiesel production by
[297] Liu B, Zhang Z, Huang K. Cellulose sulfuric acid as a bio-supported and esterication of oleic acid over Bronsted acidic ionic liquid supported onto
recyclable solid acid catalyst for the synthesis of 5-hydroxymethylfurfural Fe-incorporated SBA-15. Ind Eng Chem Res 2012;51:165906.
and 5-ethoxymethylfurfural from fructose. Cellulose 2013;20:20819. [326] Soriano NU, Venditti R, Argyropoulos DS. Biodiesel synthesis via
[298] Wang S, Zhang Z, Liu B, Li J. Silica coated magnetic Fe3O4 nanoparticles homogeneous Lewis acid-catalyzed transesterication. Fuel 2009;88:5605.
supported phosphotungstic acid: a novel environmentally friendly catalyst [327] Werpy T, Petersen G. Top value added chemicals from biomass, vol. 1. US
for the synthesis of 5-ethoxymethylfurfural from 5-hydroxymethylfurfural Department of Energy (USDOE); 2004.
and fructose. Catal Sci Technol 2013;3:210412. [328] Talebian-Kiakalaieh A, Amin NAS, Hezaveh H. Glycerol for renewable acrolein
[299] Wang H, Deng T, Wang Y, Cui X, Qi Y, Mu X, et al. Graphene oxide as a facile production by catalytic dehydration. Renew Sust Energy Rev 2014;40:2859.
acid catalyst for the one-pot conversion of carbohydrates into [329] Alhanash A, Kozhevnikova EF, Kozhevnikov IV. Gas-phase dehydration of
5-ethoxymethylfurfural. Green Chem 2013;15:237983. glycerol to acrolein catalysed by caesium heteropoly salt. Appl Catal A Gen
[300] Romn-Leshkov Y, Davis ME. Activation of carbonyl-containing molecules 2010;378:1118.
with solid Lewis acids in aqueous media. ACS Catal 2011;1:156680. [330] Gan H, Zhao X, Song B, Guo L, Zhang R, Chen C, et al. Gas phase dehydration
[301] Holm MS, Saravanamurugan S, Taarning E. Conversion of sugars to lactic acid of glycerol to acrolein catalyzed by zirconium phosphate. Chin J Catal
derivatives using heterogeneous zeotype catalysts. Science 2010;328:6025. 2014;35:114856.
[302] Holm MS, Pagn-Torres YJ, Saravanamurugan S, Riisager A, Dumesic JA, [331] Katryniok B, Paul S, Capron M, Dumeignil F. Towards the sustainable
Taarning E. Sn-Beta catalysed conversion of hemicellulosic sugars. Green production of acrolein by glycerol dehydration. ChemSusChem 2009;2:719
Chem 2012;14:7026. 30.
[303] Shimizu K, Furukawa H, Kobayashi N, Itaya Y, Satsuma A. Effects of Bronsted [332] Foo GS, Wei D, Sholl DS, Sievers C. Role of Lewis and Bronsted acid sites in
and Lewis acidities on activity and selectivity of heteropolyacid-based the dehydration of glycerol over niobia. ACS Catal 2014;4:318092.
catalysts for hydrolysis of cellobiose and cellulose. Green Chem [333] Wang Z, Wang L, Jiang Y, Hunger M, Huang J. Cooperativity of Bronsted and
2009;11:162732. Lewis acid sites on zeolite for glycerol dehydration. ACS Catal 2014;4:11447.
[304] de Clippel F, Dusselier M, Van Rompaey R, Vanelderen P, Dijkmans J, [334] Collins CD. Willey N, editor. Phytoremediation: methods and reviews, vol.
Makshina E, et al. Fast and selective sugar conversion to alkyl lactate and 23. Totowa: Humana Press Inc.; 2007. p. 99108.
180 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

[335] Xing R, Subrahmanyam AV, Olcay H, Qi W, van Walsum GP, Pendse H, et al. [365] Takagaki A, Ohara M, Nishimura S, Ebitani K. One-pot formation of furfural
Production of jet and diesel fuel range alkanes from waste hemicellulose- from xylose via isomerization and successive dehydration reactions over
derived aqueous solutions. Green Chem 2010;12:193346. heterogeneous acid and base catalysts. Chem Lett 2010;39:83840.
[336] Harvey BG, Quintana RL. Synthesis of renewable jet and diesel fuels from [366] Fang Z, Zhang F, Zeng HY, Guo F. Production of glucose by hydrolysis of
2-ethyl-1-hexene. Energy Environ Sci 2010;3:3527. cellulose at 423 K in the presence of activated hydrotalcite nanoparticles.
[337] West RM, Liu ZY, Peter M, Gartner CA, Dumesic JA. Carboncarbon bond Bioresour Technol 2011;102:801721.
formation for biomass-derived furfurals and ketones by aldol condensation [367] Takagaki A, Ohara M, Nishimura S, Ebitani K. A one-pot reaction for
in a biphasic system. J Mol Catal A Chem 2008;296:1827. biorenery: combination of solid acid and base catalysts for direct production
[338] Huber GW, Chheda JN, Barrett CJ, Dumesic JA. Production of liquid alkanes of 5-hydroxymethylfurfural from saccharides. Chem Commun 2009;62768.
by aqueous-phase processing of biomass-derived carbohydrates. Science [368] Ohara M, Takagaki A, Nishimura S, Ebitani K. Syntheses of 5-
2005;308:144650. hydroxymethylfurfural and levoglucosan by selective dehydration of glucose
[339] Subrahmanyam AV, Thayumanavan S, Huber GW. CC bond formation using solid acid and base catalysts. Appl Catal A Gen 2010;383:14955.
reactions for biomass-derived molecules. ChemSusChem 2010;3:115861. [369] Shirotori M, Nishimura S, Ebitani K. One-pot synthesis of furfural from xylose
[340] Sdaba I, Ojeda M, Mariscal R, Fierro JLG, Granados ML. Catalytic and using Al2O3NiAl layered double hydroxide acid-base bi-functional catalyst
structural properties of co-precipitated MgZr mixed oxides for furfural and sulfonated resin. Chem Lett 2016;45:1946.
valorization via aqueous aldol condensation with acetone. Appl Catal B: [370] Tuteja J, Nishimura S, Ebitani K. One-pot synthesis of furans from various
Environ 2011;101:63848. saccharides using a combination of solid acid and base catalysts. Bull Chem
[341] Xu WJ, Liu XH, Ren JW, Liu HH, Ma YC, Wang YQ, et al. Synthesis of nanosized Soc Jpn 2012;85:27581.
mesoporous CoAl spinel and its application as solid base catalyst. Micropor [371] Yue C, Rigutto MS, Hensen EJM. Glucose dehydration to 5-
Mesopor Mater 2011;142:2517. hydroxymethylfurfural by a combination of a basic zirconosilicate and a solid
[342] Shen WQ, Tompsett GA, Hammond KD, Xing R, Dogan F, Grey CP, et al. Liquid acid. Catal Lett 2014;144:21218.
phase aldol condensation reactions with MgOZrO2 and shape-selective [372] Son PA, Nishimura S, Ebitani K. Preparation of zirconium carbonate as
nitrogen-substituted NaY. Appl Catal A Gen 2011;392:5768. water-tolerant solid base catalyst for glucose isomerization and one-pot
[343] West RM, Liu ZY, Peter M, Dumesic JA. Liquid alkanes with targeted molecular synthesis of levulinic acid with solid acid catalyst. Reac Kinet Mech Cat
weights from biomass-derived carbohydrates. ChemSusChem 2008;1:417 2014;111:18397.
24. [373] Prez-Maqueda J, Arenas-Ligioiz I, Lpez , Fernndez-Bolaos JG. Eco-
[344] Kikhtyanin O, Kelbichov V, Vitvarov D, Kubu M, Kubicka D. Aldol friendly preparation of 5-hydroxymethylfurfural from sucrose using ion-
condensation of furfural and acetone on zeolites. Catal Today 2014;227:154 exchange resins. Chem Eng Sci 2014;109:24450.
62. [374] Peng WH, Lee YY, Wu C, Wu KC-W. Acidbase bi-functionalized, large-pored
[345] Kikhtyanin O, Chlubn P, Jindrov T, Kubicka D. Peculiar behavior of MWW mesoporous silica nanoparticles for cooperative catalysis of one-pot
materials in aldol condensation of furfural and acetone. Dalton Trans cellulose-to-HMF conversion. J Mater Chem 2012;22:231815.
2014;43:1062841. [375] Wang L, Wang H, Liu F, Zheng A, Zhang J, Sun Q, et al. Selective catalytic
[346] Kikhtyanin O, Kubicka D, Cejka J. Toward understanding of the role of Lewis production of 5-hydroxymethylfurfural from glucose by adjusting catalyst
acidity in aldol condensation of acetone and furfural using MOF and zeolite wettability. ChemSusChem 2014;7:4026.
catalysts. Catal Today 2015;243:15862. [376] Li H, Govind KS, Kotni R, Shunmugavel S, Riisager A, Yang S. Direct catalytic
[347] Corma A, de la Torre O, Renz M. High-quality diesel from hexose- and transformation of carbohydrates into 5-ethoxymethylfurfural with acidbase
pentose-derived biomass platform molecules. ChemSusChem 2011;4:15747. bifunctional hybrid nanospheres. Energy Conv Manag 2014;88:124551.
[348] Corma A, de la Torre O, Renz M, Villandier N. Production of high-quality diesel [377] Hao W, Li W, Tang X, Zeng X, Sun Y, Liu S, et al. Catalytic transfer
from biomass waste products. Angew Chem 2011;123:24236. hydrogenation of biomass-derived 5-hydroxymethyl furfural to the building
[349] Corma A, de la Torre O, Renz M. Production of high quality diesel from block 2, 5-bishydroxymethyl furan. Green Chem 2016;18:10808.
cellulose and hemicellulose by the Sylvan process: catalysts and process [378] Jae J, Mahmoud E, Lobo RF, Vlachos DG. Cascade of liquid-phase catalytic
variables. Energy Environ Sci 2012;5:632844. transfer hydrogenation and etherication of 5-hydroxymethylfurfural to
[350] Li G, Li N, Yang J, Wang A, Wang X, Cong Y, et al. Synthesis of renewable diesel potential biodiesel components over Lewis acid zeolites. ChemCatChem
with the 2-methylfuran, butanal and acetone derived from lignocellulose. 2014;6:50813.
Bioresour Technol 2013;134:6672. [379] Lewis JD, Van de Vyver S, Crisci AJ, Gunther WR, Michaelis VK, Grin RG,
[351] Li G, Li N, Li S, Wang A, Cong Y, Wang X, et al. Synthesis of renewable diesel et al. A continuous ow strategy for the coupled transfer hydrogenation and
with hydroxyacetone and 2-methyl-furan. Chem Commun 2013;49:5727 etherication of 5-(hydroxymethyl) furfural using Lewis acid zeolites.
9. ChemSusChem 2014;7:225565.
[352] Bond JQ, Upadhye AA, Olcay H, Tompsett GA, Jae J, Xing R, et al. Production [380] Song J, Zhou B, Zhou H, Wu L, Meng Q, Liu Z, et al. Porous zirconiumphytic
of renewable jet fuel range alkanes and commodity chemicals from integrated acid hybrid: a highly ecient catalyst for MeerweinPonndorfVerley
catalytic processing of biomass. Energy Environ Sci 2014;7:150023. reductions. Angew Chem 2015;127:95315.
[353] Li G, Li N, Wang Z, Li C, Wang A, Wang X, et al. Synthesis of high-quality diesel [381] Demma Car P, Ciriminna R, Shiju NR, Rothenberg G, Pagliaro M. Enhanced
with furfural and 2-methylfuran from hemicellulose. ChemSusChem heterogeneous catalytic conversion of furfuryl alcohol into butyl levulinate.
2012;5:195866. ChemSusChem 2014;7:83540.
[354] Gelman F, Blum J, Avnir D. Acids and bases in one pot while avoiding their [382] Lu B, An S, Song D, Su F, Yang X, Guo Y. Design of organosulfonic acid
mutual destruction. Angew Chem 2001;113:375961. functionalized organosilica hollow nanospheres for ecient conversion of
[355] Li H, Wu H, Zhang Q, Liu J, Liu X, Liu Y, et al. Solid acid-base bifunctional furfural alcohol to ethyl levulinate. Green Chem 2015;17:176778.
catalysts in organic transformations. Curr Catal 2013;2:173212. [383] Kaur N, Ali A. Lithium zirconate as solid catalyst for simultaneous
[356] Watanabe M, Aizawa Y, Iida T, Aida TM, Levy C, Sue K, et al. Glucose reactions esterication and transesterication of low quality triglycerides. Appl Catal
with acid and base catalysts in hot compressed water at 473K. Carbohyd Res A Gen 2015;489:193202.
2005;340:192530. [384] Rattanaphra D, Harvey A, Srinophakun P. Simultaneous conversion of
[357] Daorattanachai P, Namuangruk S, Viriya-empikul N, Laosiripojana N, triglyceride/free fatty acid mixtures into biodiesel using sulfated zirconia.
Faungnawakij K. 5-Hydroxymethylfurfural production from sugars and Top Catal 2010;53:77382.
cellulose in acid-and base-catalyzed conditions under hot compressed water. [385] Yan S, Salley SO, Ng KYS. Simultaneous transesterication and esterication
J Ind Eng Chem 2012;18:1893901. of unrened or waste oils over ZnO-La2O3 catalysts. Appl Catal A Gen
[358] Watanabe M, Aizawa Y, Iida T, Nishimura R, Inomata H. Catalytic glucose and 2009;353:20312.
fructose conversions with TiO2 and ZrO2 in water at 473K: relationship [386] Lee HV, Juan JC, Tauq-Yap YH. Preparation and application of binary
between reactivity and acidbase property determined by TPD measurement. acid-base CaO-La 2 O 3 catalyst for biodiesel production. Renew Energy
Appl Catal A Gen 2005;295:1506. 2015;74:12432.
[359] Qi X, Watanabe M, Aida TM, Smith RL Jr. Catalytical conversion of fructose [387] Benvenuti F, Carlini C, Patrono P, Galletti AMR, Sbrana G, Massucci MA, et al.
and glucose into 5-hydroxymethylfurfural in hot compressed water by Heterogeneous zirconium and titanium catalysts for the selective synthesis
microwave heating. Catal Commun 2008;9:22449. of 5-hydroxymethyl-2-furaldehyde from carbohydrates. Appl Catal A Gen
[360] Yang L, Liu Y, Ruan R. Hydrolysis of glucose to 5-hydroxymethylfurfural. Adv 2000;193:14753.
Mater Res 2011;335-6:144853. [388] Qi X, Guo H, Li L. Ecient conversion of fructose to 5-hydroxymethylfurfural
[361] Qi X, Watanabe M, Aida TM, Smith RL Jr. Sulfated zirconia as a solid acid catalyzed by sulfated zirconia in ionic liquids. Ind Eng Chem Res
catalyst for the dehydration of fructose to 5-hydroxymethylfurfural. Catal 2011;50:79859.
Commun 2009;10:17715. [389] Moreau C, Durand R, Roux A, Tichit D. Isomerization of glucose into fructose
[362] Yan H, Yang Y, Tong D, Hu C, Abu-Omar MM. Catalytic conversion of glucose in the presence of cation-exchanged zeolites and hydrotalcites. Appl Catal
to 5-hydroxymethylfurfural over SO42/ZrO2 and SO42/ZrO2Al2O3 solid acid A Gen 2000;193:25764.
catalysts. Catal Commun 2009;10:155863. [390] Qu YS, Song YL, Huang CP, Zhang J, Chen BH. Alkaline ionic liquids as catalysts:
[363] Yang Y, Xiang X, Tong D, Hu C, Abu-Omar MM. One-pot synthesis of a novel and green process for the dehydration of carbohydrates to give
5-hydroxymethylfurfural directly from starch over/ZrO2Al2O3 solid catalyst. 5-hydroxymethylfurfural. Ind Eng Chem Res 2012;51:1300813.
Bioresour Technol 2012;116:3026. [391] Zhao Q, Sun Z, Wang S, Huang G, Wang X, Jiang Z. Conversion of highly
[364] Osatiashtiani A, Lee AF, Brown DR, Melero JA, Moralese G, Wilson K. concentrated fructose into 5-hydroxymethylfurfural by acidbase bifunctional
Bifunctional SO 4 /ZrO 2 catalysts for 5-hydroxymethylfufural (5-HMF) HPA nanocatalysts induced by choline chloride. RSC Adv 2014;4:63055
production from glucose. Catal Sci Technol 2014;4:33342. 61.
H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194 181

[392] Liu FJ, Kong WP, Qi CZ, Zhu LF, Xiao FS. Design and synthesis of mesoporous production from glycerol steam reforming. Int J Hydrogen Energy
polymer-based solid acid catalysts with excellent hydrophobicity and 2014;39:570412.
extraordinary catalytic activity. ACS Catal 2012;2:56572. [422] Shirotori M, Nishimura S, Ebitani K. One-pot synthesis of furfural derivatives
[393] Li H, Saravanamurugan S, Yang S, Riisager A. Direct transformation of from pentoses using solid acid and base catalysts. Catal Sci Technol
carbohydrates to the biofuel 5-ethoxymethylfurfural by solid acid catalysts. 2014;4:9718.
Green Chem 2016;18:72634. [423] Elmekawy AA, Shiju NR, Rothenberg G, Brown DR. Environmentally benign
[394] Ruppert AM, Meeldijk JD, Kuipers BWM, Ern BH, Weckhuysen BM. Glycerol bifunctional solid acid and base catalysts. Ind Eng Chem Res 2014;53:18722
etherication over highly active CaO-based materials: new mechanistic 8.
aspects and related colloidal particle formation. Chem Eur J 2008;14:201624. [424] Lauwaert J, De Canck E, Esquivel D, Van Der Voort P, Thybaut JW, Marina
[395] Calatayud M, Ruppert AM, Weckhuysen BM. Theoretical study on the role GB. Catal Today 2015;246:3545.
of surface basicity and Lewis acidity on the etherication of glycerol over [425] De S, Saha B, Luque R. Hydrodeoxygenation processes: advances on catalytic
alkaline earth metal oxides. Chem Eur J 2009;15:1086470. transformations of biomass-derived platform chemicals into hydrocarbon
[396] Sivaiah MV, Robles-Manuel S, Valange S, Barrault J. Recent developments in fuels. Bioresour Technol 2015;178:10818.
acid and base-catalyzed etherication of glycerol to polyglycerols. Catal Today [426] Lee J, Kim YT, Huber GW. Aqueous-phase hydrogenation and
2012;198:30513. hydrodeoxygenation of biomass-derived oxygenates with bimetallic catalysts.
[397] Gilkey MJ, Xu B. Heterogeneous catalytic transfer hydrogenation as an Green Chem 2014;16:70818.
effective pathway in biomass upgrading. ACS Catal 2016;6:142036. [427] Slade JH, Knopf DA. Heterogeneous OH oxidation of biomass burning organic
[398] Weber N, Weitkamp P, Mukherjee KD. Fatty acid steryl, stanyl, and steroid aerosol surrogate compounds: assessment of volatilisation products and the
esters by esterication and transesterication in vacuo using Candida rugosa role of OH concentration on the reactive uptake kinetics. Phys Chem Chem
lipase as catalyst. J Agric Food Chem 2001;49:6771. Phys 2013;15:5898915.
[399] Roy I, Gupta MN. Non-thermal effects of microwaves on protease-catalyzed [428] Li H, Zhang Q, Riisager A, Yang S. Catalytic valorization of cellulose and
esterication and transesterication. Tetrahedron 2003;59:54316. cellobiose with nanoparticles. Curr Nanosci 2015;11:114.
[400] Alsalme A, Kozhevnikova EF, Kozhevnikov IV. Heteropoly acids as catalysts [429] Zope BN, Hibbitts DD, Neurock M, Davis RJ. Reactivity of the gold/water
for liquid-phase esterication and transesterication. Appl Catal A Gen interface during selective oxidation catalysis. Science 2010;330:748.
2008;349:1706. [430] Silva B, Figueiredo H, Soares OSGP, Pereira MFR, Figueiredo JL, Lewandowska
[401] Xu L, Wang Y, Yang X, Hu J, Li W, Guo Y. Simultaneous esterication and AE, et al. Evaluation of ion exchange-modied Y and ZSM5 zeolites in Cr(VI)
transesterication of soybean oil with methanol catalyzed by mesoporous biosorption and catalytic oxidation of ethyl acetate. Appl Catal B: Environ
Ta2O5/SiO2[H3PW12O40/R] (R:Me or Ph) hybrid catalysts. Green Chem 2012;117-8:40613.
2009;11:31417. [431] Abad A, Concepcin P, Corma A, Garca H. A collaborative effect between gold
[402] Srilatha K, Issariyakul T, Lingaiah N, Sai Prasad PS, Kozinski J, Dalai AK. and a support induces the selective oxidation of alcohols. Angew Chem Int
Ecient esterication and transesterication of used cooking oil Ed 2005;44:40669.
using 12-tungstophosphoric acid (TPA)/Nb 2 O 5 catalyst. Energy Fuels [432] Deng W, Zhang Q, Wang Y. Catalytic transformations of cellulose and
2010;24:474855. cellulose-derived carbohydrates into organic acids. Catal Today 2014;234:31
[403] Garcia CM, Teixeira S, Marciniuk LL, Schuchardt U. Transesterication of 41.
soybean oil catalyzed by sulfated zirconia. Bioresour Technol 2008;99:6608 [433] Zhang J, Li J, Tang Y, Lin L, Long M. Advances in catalytic production of
13. bio-based polyester monomer 2,5-furandicarboxylic acid derived from
[404] Hoydonckx HE, De Vos DE, Chavan SA, Jacobs PA. Esterication and lignocellulosic biomass. Carbohyd Polym 2015;130:4208.
transesterication of renewable chemicals. Top Catal 2004;27:8396. [434] Cao Q, Dornan LM, Rogan L, Hughes NL, Muldoon MJ. Aerobic oxidation
[405] Lien YS, Hsieh LS, Wu JCS. Biodiesel synthesis by simultaneous esterication catalysis with stable radicals. Chem Commun 2014;50:452443.
and transesterication using oleophilic acid catalyst. Ind Eng Chem Res [435] Grasset FL, Katryniok B, Paul S, Nardello-Rataj V, Pera-Titus M, Clacens JM,
2010;49:211821. et al. Selective oxidation of 5-hydroxymethylfurfural to 2,5- diformylfuran
[406] Boz N, Degirmenbasi N, Kalyon DM. Esterication and transesterication of over intercalated vanadium phosphate oxides. RSC Adv 2013;3:9942
waste cooking oil over Amberlyst 15 and modied Amberlyst 15 catalysts. 8.
Appl Catal B: Environ 2015;165:72330. [436] Gong Y, Lin L. Oxidative decarboxylation of levulinic acid by silver(I)/
[407] Jimnez-Morales I, Santamara-Gonzlez J, Maireles-Torres P, Jimnez-Lpez persulfate. Molecules 2011;16:271425.
A. Calcined zirconium sulfate supported on MCM-41 silica as acid catalyst [437] Besson M, Lahmer F, Gallezot P, Fuertes P, Flche G. Catalytic oxidation of
for ethanolysis of sunower oil. Appl Catal B: Environ 2011;103:918. glucose on bismuth-promoted palladium catalysts. J Catal 1995;152:116
[408] Tamilarasan S, Sahadevan R. Ultrasonic assisted acid base transesterication 21.
of algal oil from marine macroalgae Caulerpa peltata: optimization and [438] Delidovich IV, Taran OP, Matvienko LG, Simonov AN, Simakova IL,
characterization studies. Fuel 2014;128:34755. Bobrovskaya AN, et al. Selective oxidation of glucose over carbon-supported
[409] Ngo HL, Zaropoulos NA, Foglia TA, Samulski ET, Lin W. Ecient two-step Pd and Pt catalysts. Catal Lett 2010;140:1421.
synthesis of biodiesel from greases. Energy Fuels 2007;22:62634. [439] Besson M, Gallezot P. Selective oxidation of alcohols and aldehydes on metal
[410] Li Y, He D, Yuan Y, Cheng Z, Zhu Q. Inuence of acidic and basic properties catalysts. Catal Today 2000;57:12741.
of ZrO2 based catalysts on isosynthesis. Fuel 2002;81:161117. [440] Sakurai H, Koga K, Kiuchi M. Gold nanoparticles deposited on Amberlyst-15:
[411] Lpez DE, Goodwin JG, Bruce DA, Furuta S. Esterication and metalacid bifunctional catalyst for cellobiose conversion to gluconic acid.
transesterication using modied-zirconia catalysts. Appl Catal A Gen Catal Today 2015;251:96102.
2008;339:7683. [441] Baatz C, Pre U. Preparation of gold catalysts for glucose oxidation by
[412] Kim M, DiMaggio C, Yan S, Salley SO, Ng KYS. The synergistic effect of alcohol incipient wetness. J Catal 2007;249:3440.
mixtures on transesterication of soybean oil using homogeneous and [442] Witonska I, Frajtak M, Karski S. Selective oxidation of glucose to gluconic
heterogeneous catalysts. Appl Catal A Gen 2010;378:13443. acid over PdTe supported catalysts. Appl Catal A Gen 2011;401:7382.
[413] Perego C, Bianchi D. Biomass upgrading through acidbase catalysis. Chem [443] Amaniampong PN, Jia X, Wang B, Mushrif SH, Borgna A, Yang Y. Catalytic
Eng J 2010;161:31422. oxidation of cellobiose over TiO 2 supported gold-based bimetallic
[414] Sun J, Zhu K, Gao F, Wang C, Liu J, Peden CHF, et al. Direct conversion of nanoparticles. Catal Sci Technol 2015;5:2393405.
bio-ethanol to isobutene on nanosized ZnxZryOz mixed oxides with balanced [444] Pre U, Herrmann M, Baatz C, Decker N. Gold-catalyzed selective glucose
acidbase sites. J Am Chem Soc 2011;133:110969. oxidation at high glucose concentrations and oxygen partial pressures. Appl
[415] Nakajima T, Nameta H, Mishima S, Matsuzaki I, Tanabe K. A highly active Catal A Gen 2011;406:8993.
and highly selective oxide catalyst for the conversion of ethanol to acetone [445] Rautiainen S, Lehtinen P, Vehkamki M, Niemel K, Kemell M, Heikkil M,
in the presence of water vapour. J Mater Chem 1994;4:8538. et al. Microwave-assisted base-free oxidation of glucose on gold nanoparticle
[416] Hutchings GJ, Johnston P, Lee DF, Williams CD. Acetone conversion to catalysts. Catal Commun 2016;74:11518.
isobutene in high selectivity using zeolite catalyst. Catal Lett 1993;21:4953. [446] Wojcieszak R, Cuccovia IM, Silva MA, Rossi LM. Selective oxidation of glucose
[417] Tao LZ, Chai SH, Wang HP, Yan B, Liang Y, Xu BQ. Comparison of gas-phase to glucuronic acid by cesium-promoted gold nanoparticle catalyst. J Mol Catal
dehydration of propane polyols over solid acidbase catalysts. Catal Today A Chem 2016;doi:10.1016/j.molcata.2016.02.008.
2014;234:23744. [447] Albert J, Wlfel R, Bsmann A, Wasserscheid P. Selective oxidation of complex,
[418] Stoic D, Bennici S, Couturier JL, Dubois JL, Auroux A. Inuence of surface water-insoluble biomass to formic acid using additives as reaction
acidbase properties of zirconia and titania based catalysts on the product accelerators. Energy Environ Sci 2012;5:795662.
selectivity in gas phase dehydration of glycerol. Catal Commun 2012;17:238. [448] Wlfel R, Taccardi N, Bosmann A, Wasserscheid P. Selective catalytic
[419] Climent MJ, Corma A, De Frutos P, Iborra S, Noy M, Velty A, et al. Chemicals conversion of biobased carbohydrates to formic acid using molecular oxygen.
from biomass: synthesis of glycerol carbonate by transesterication and Green Chem 2011;13:275963.
carbonylation with urea with hydrotalcite catalysts. The role of acidbase [449] Li J, Ding DJ, Deng L, Guo QX, Fu Y. Catalytic air oxidation of biomass-derived
pairs. J Catal 2010;269:1409. carbohydrates to formic acid. ChemSusChem 2012;5:131318.
[420] Prez-Barrado E, Pujol MC, Aguil M, Llorca J, Cesteros Y, Daz F, et al. [450] Niu M, Hou Y, Ren S, Wang W, Zheng Q, Wu W. The relationship between
Inuence of acidbase properties of calcined MgAl and CaAl layered double oxidation and hydrolysis in the conversion of cellulose in NaVO3H2SO4
hydroxides on the catalytic glycerol etherication to short-chain polyglycerols. aqueous solution with O2. Green Chem 2015;17:33542.
Chem Eng J 2015;264:54756. [451] Niu M, Hou Y, Ren S, Wu W, Marsh KN. Conversion of wheat straw into formic
[421] Bobadilla LF, Penkova A, Romero-Sarria F, Centeno MA, Odriozola JA. Inuence acid in NaVO3H2SO4 aqueous solution with molecular oxygen. Green Chem
of the acid-base properties over NiSn/MgO-Al2O3 catalysts in the hydrogen 2015;17:4539.
182 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

[452] Wang W, Niu M, Hou Y, Wu W, Liu Z, Liu Q, et al. Catalytic conversion of under benign reaction conditions. Appl Catal A Gen 2013;456:44
biomass-derived carbohydrates to formic acid using molecular oxygen. Green 50.
Chem 2014;16:261418. [481] Sheldon RA. Selective catalytic synthesis of ne chemicals: opportunities and
[453] Xu J, Zhang H, Zhao Y, Yang Z, Yu B, Xua H, et al. Heteropolyanion-based ionic trends. J Mol Catal A Chem 1996;107:7583.
liquids catalysed conversion of cellulose into formic acid without any [482] Smith MB, March J. Marchs advanced organic chemistry: reactions,
additives. Green Chem 2014;16:49315. mechanisms, and structure. 5th ed. New York: Wiley & Sons; 2000.
[454] Tang Z, Deng W, Wang Y, Zhu E, Wan X, Zhang Q, et al. Transformation of [483] Vinke P, van Dama HE, van Bekkum H. Platinum catalyzed oxidation of
cellulose and its derived carbohydrates into formic and lactic acids catalyzed 5-hydroxymethylfurfural. Stud Surf Sci Catal 1990;55:14758.
by vanadyl cations. ChemSusChem 2014;7:155767. [484] Vinke P, van der Poel W, van Bekkum H. On the oxygen tolerance of noble
[455] Zhang J, Sun M, Liu X, Han Y. Catalytic oxidative conversion of cellulosic metal catalysts in liquid phase alcohol oxidations the inuence of the support
biomass to formic acid and acetic acid with exceptionally high yields. Catal on catalyst deactivation. Stud Surf Sci Catal 1991;59:38594.
Today 2014;233:7782. [485] Gorbanev YY, Kegns S, Riisager A. Effect of support in heterogeneous
[456] Zhang J, Liu X, Sun M, Ma X, Han Y. Direct conversion of cellulose to glycolic ruthenium catalysts used for the selective aerobic oxidation of HMF in water.
acid with a phosphomolybdic acid catalyst in a water medium. ACS Catal Top Catal 2011;54:131824.
2012;2:1698702. [486] Sthlberg T, Eyjlfsdttir E, Gorbanev YY, Sdaba I, Riisager A. Aerobic
[457] Zhang J, Sun M, Han Y. Selective oxidation of glycerol to formic acid in highly oxidation of 5-(hydroxymethyl)furfural in ionic liquids with solid ruthenium
concentrated aqueous solutions with molecular oxygen using V-substituted hydroxide catalysts. Catal Lett 2012;142:108997.
phosphomolybdic acids. RSC Adv 2014;4:354636. [487] Gorbanev YY, Klitgaard SK, Woodley JM, Christensen CH, Riisager A. Gold-
[458] Xu J, Zhao Y, Xu H, Zhang H, Yu B, Hao L, et al. Selective oxidation of glycerol catalyzed aerobic oxidation of 5-hydroxymethylfurfural in water at ambient
to formic acid catalyzed by Ru(OH)4/r-GO in the presence of FeCl3. Appl Catal temperature. ChemSusChem 2009;2:6725.
B: Environ 2014;154-5:26773. [488] Casanova O, Iborra S, Corma A. Biomass into chemicals: aerobic oxidation
[459] Kapkowski M, Bartczak P, Korzec M, Sitko R, Szade J, Balin K, et al. SiO2-, Cu-, of 5-hydroxymethyl-2-furfural into 2,5-furandicarboxylic acid with gold
and Ni-supported Au nanoparticles for selective glycerol oxidation in the nanoparticle catalysts. ChemSusChem 2009;2:113844.
liquid phase. J Catal 2014;319:11018. [489] Zope BN, Davis SE, Davis RJ. Inuence of reaction conditions on
[460] Manas MG, Campos J, Sharninghausen LS, Lin E, Crabtree RH. Selective diacid formation during Au-catalyzed oxidation of glycerol and
catalytic oxidation of sugar alcohols to lactic acid. Green Chem 2015;17:594 hydroxymethylfurfural. Top Catal 2012;55:2432.
600. [490] Gupta NK, Nishimura S, Takagaki A, Ebitani K. Hydrotalcite-supported
[461] Maris EP, Davis RJ. Hydrogenolysis of glycerol over carbon-supported Ru and gold-nanoparticle-catalyzed highly ecient base-free aqueous oxidation of
Pt catalysts. J Catal 2007;249:32837. 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid under atmospheric
[462] Maris EP, Ketchie WC, Murayama M, Davis RJ. Glycerol hydrogenolysis on oxygen pressure. Green Chem 2011;13:8247.
carbon-supported PtRu and AuRu bimetallic catalysts. J Catal 2007;251:281 [491] Pasini T, Piccinini M, Blosi M, Bonelli R, Albonetti S, Dimitratos N, et al.
94. Selective oxidation of 5-hydroxymethyl-2-furfural using supported gold-
[463] Wang X, Song Y, Huang C, Liang F, Chen B. Lactic acid production from glucose copper nanoparticles. Green Chem 2011;13:20919.
over polymer catalysts in aqueous alkaline solution under mild conditions. [492] Wan X, Zhou C, Chen J, Deng W, Zhang Q, Yang Y, et al. Base-free aerobic
Green Chem 2014;16:423440. oxidation of 5-hydroxymethyl-furfural to 2,5-furandicarboxylic acid in water
[464] Biella S, Prati L, Rossi M. Selective oxidation of D-glucose on gold catalyst. J catalyzed by functionalized carbon nanotube-supported AuPd alloy
Catal 2002;206:2427. nanoparticles. ACS Catal 2014;4:217585.
[465] Ishida T, Kinoshita N, Okatsu H, Akita T, Takei T, Haruta M. Inuence of the [493] Albonetti S, Lolli A, Morandi V, Migliori A, Lucarelli C, Cavani F. Conversion
support and the size of gold clusters on catalytic activity for glucose oxidation. of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid over Au-based
Angew Chem Int Ed 2008;47:92658. catalysts: optimization of active phaseand metalsupport interaction. Appl
[466] Katryniok B, Kimura H, Skrzynska E, Girardon JS, Fongarland P, Capron M, Catal B: Environ 2015;163:52030.
et al. Selective catalytic oxidation of glycerol: perspectives for high value [494] Davis SE, Houk LR, Tamargo EC, Datye AK, Davis RJ. Oxidation of
chemicals. Green Chem 2011;13:196079. 5-hydroxymethylfurfural over supported Pt, Pd and Au catalysts. Catal Today
[467] Li H, Kotni R, Zhang Q, Shunmugavel S, Yang S. Chemoselective oxidation 2011;160:5560.
of bio-glycerol with nano-sized metal catalysts. Mini-Rev Org Chem [495] Saha B, Dutta S, Abu-Omar MM. Aerobic oxidation of 5-
2015;12:16277. hydroxylmethylfurfural with homogeneous and nanoparticulate catalysts.
[468] Zhou CH, Zhao H, Tong DS, Wu LM, Yu WH. Recent advances in catalytic Catal Sci Technol 2012;2:7981.
conversion of glycerol. Catal Rev 2013;55:369453. [496] Lilga MA, Hallen RT, Gray M. Production of oxidized derivatives of
[469] Dusselier M, Wouwe PV, Dewaele A, Makshina E, Sels BF. Lactic acid as a 5-hydroxymethylfurfural (HMF). Top Catal 2010;53:12649.
platform chemical in the biobased economy: the role of chemocatalysis. [497] Krger M, Pre U, Vorlop KD. A new approach for the production of
Energy Environ Sci 2013;6:141542. 2,5-furandicarboxylic acid by in-situ oxidation of 5-hydroxymethylfurfural
[470] Wang Y, Deng W, Wang B, Zhang Q, Wan X, Tang Z, et al. Chemical synthesis starting from fructose. Top Catal 2000;13:23742.
of lactic acid from cellulose catalysed by lead(II) ions in water. Nat Commun [498] Ribeiro ML, Schuchardt U. Cooperative effect of cobalt acetylacetonate and
2013;4:21417. silica in the catalytic cyclization and oxidation of fructose to 2,5-
[471] Wang FF, Liu CL, Dong WS. Highly ecient production of lactic acid from furandicarboxylic acid. Catal Commun 2003;4:836.
cellulose using lanthanide triate catalysts. Green Chem 2013;15:20915. [499] Saha B, Gupta D, Abu-Omar MM, Modak A, Bhaumik A. Porphyrin-based
[472] Bermejo-Deval R, Assary RS, Nikolla E, Moliner M, Romn-Leshkov Y, Hwang porous organic polymer-supported iron(III) catalyst for ecient aerobic
SJ, et al. Metalloenzyme-like catalyzed isomerizations of sugars by Lewis acid oxidation of 5-hydroxymethyl-furfural into 2,5-furandicarboxylic acid. J Catal
zeolites. Proc Natl Acad Sci USA 2012;109:972732. 2013;299:31620.
[473] Huo Z, Fang Y, Ren D, Zhang S, Yao G, Zeng X, et al. Selective conversion of [500] Gao L, Deng K, Zheng J, Liu B, Zhang Z. Ecient oxidation of biomass derived
glucose into lactic acid with transition metal ions in diluted aqueous NaOH 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid catalyzed by
solution. ACS Sust Chem Eng 2014;2:276571. Merrield resin supported cobalt porphyrin. Chem Eng J 2015;270:4449.
[474] Mei N, Liu B, Zheng J, Lv K, Tang D, Zhang Z. A novel magnetic palladium [501] Siyo B, Schneider M, Pohl MM, Langer P, Steinfeldt N. Synthesis,
catalyst for the mild aerobic oxidation of 5-hydroxymethylfurfural into characterization, and application of PVP-Pd NP in the aerobic oxidation of
2,5-furandicarboxylic acid in water. Catal Sci Technol 2015;5:3194202. 5-hydroxymethylfurfural (HMF). Catal Lett 2014;144:498506.
[475] Vasiliu M, Jones AJ, Guynn K, Dixon DA. Prediction of the thermodynamic [502] Sahu R, Dhepe PL. Synthesis of 2,5-furandicarboxylic acid by the aerobic
properties of key products and intermediates from biomass II. J Phys Chem oxidation of 5-hydroxymethyl furfural over supported metal catalysts. React
C 2012;116:2073854. Kinet Mech Cat 2014;112:17387.
[476] Tsanaktsis V, Vouvoudi E, Papageorgiou GZ, Papageorgiou DG, Chrissas K, [503] Jain A, Jonnalagadda SC, Ramanujachary KV, Mugweru A. Selective oxidation
Bikiaris DN. Thermal degradation kinetics and decomposition mechanism of 5-hydroxymethyl-2-furfural to furan-2,5-dicarboxylic acid over spinel
of polyesters based on 2,5-furandicarboxylic acid and low molecular weight mixed metal oxide catalyst. Catal Commun 2015;58:17982.
aliphatic diols. J Anal Appl Pyrol 2014;112:36978. [504] Rass HA, Essayem N, Besson M. Selective aerobic oxidation of 5-HMF into
[477] Wilsens CHRM, Verhoeven JMGA, Noordover BAJ, Hansen MR, Auhl D, Rastogi 2,5-furandicarboxylic acid with pt catalysts supported on TiO2- and ZrO2-
S. Thermotropic polyesters from 2,5-furandicarboxylic acid and vanillic acid: based supports. ChemSusChem 2015;7:120617.
synthesis, thermal properties, melt behavior, and mechanical performance. [505] Liu B, Ren Y, Zhang Z. Aerobic oxidation of 5-hydroxymethylfurfural into
Macromolecules 2014;47:330616. 2,5-furandicarboxylic acid in water under mild conditions. Green Chem
[478] Wu B, Xu Y, Bu Z, Wu L, Li BG, Dubois P. Biobased poly(butylene 2015;17:161017.
2,5-furandicarboxylate) and poly(butylene adipate-co-butylene [506] Zhang Z, Zhen J, Liu B, Lv K, Deng K. Selective aerobic oxidation of the
2,5-furandicarboxylate)s: from synthesis using highly puried 2,5- biomass-derived precursor 5-hydroxymethylfurfural to 2,5-furandicarboxylic
furandicarboxylic acid to thermo-mechanical properties. Polymer (Guildf) acid under mild conditions over a magnetic palladium nanocatalyst. Green
2014;55:364855. Chem 2015;17:130817.
[479] Wahlen J, Moens B, De Vos DE, Alsters PL, Jacobs PA. Titanium silicalite 1 [507] Wang S, Zhang Z, Liu B. Catalytic conversion of fructose and
(TS-1) catalyzed oxidative transformations of furan derivatives with hydrogen 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid over a recyclable
peroxide. Adv Synth Catal 2004;346:3338. Fe3O4CoOx magnetite nanocatalyst. ACS Sust Chem Eng 2015;3:40612.
[480] Hansen TS, Sdaba I, Garca-Surez EJ, Riisager A. Cu catalyzed oxidation of [508] Partenheimer W, Grushin VV. Synthesis of 2,5-diformylfuran and furan-2,5-
5-hydroxymethylfurfural to 2,5-diformylfuran and 2,5-furandicarboxylic acid dicarboxylic acid by catalytic air-oxidation of 5-hydroxymethylfurfural:
H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194 183

unexpectedly selective aerobic oxidation of benzyl alcohol to benzaldehyde [536] Zhang Z, Yuan Z, Tang D, Ren Y, Lv K, Liu B. Iron oxide encapsulated by
with metal/bromide catalysts. Adv Synth Catal 2001;343:10211. ruthenium hydroxyapatite as heterogeneous catalyst for the synthesis of
[509] Navarro OC, Cans AC, Chornet SI. Chemicals from biomass: aerobic oxidation 2,5-diformylfuran. ChemSusChem 2014;7:3496504.
of 5-hydroxymethyl-2-furaldehyde into diformylfurane catalyzed [537] Wang S, Zhang Z, Liu B, Li J. Environmentally friendly oxidation of biomass
by immobilized vanadyl-pyridine complexes on polymeric and derived 5-hydroxymethylfurfural into 2,5-diformylfuran catalyzed by
organofunctionalized mesoporous supports. Top Catal 2009;52:30414. magnetic separation of ruthenium catalyst. Ind Eng Chem Res 2014;53:5820
[510] Carlini C, Patrono P, Raspolli Galletti AM, Sbrana G, Zima V. Selective oxidation 7.
of 5-hydroxymethyl-2-furaldehyde to furan-2,5-dicarboxaldehyde by catalytic [538] Du Z, Ma J, Wang F, Liu J, Xu J. Oxidation of 5-hydroxymethylfurfural to maleic
systems based on vanadyl phosphate. Appl Catal A Gen 2005;289:197204. anhydride with molecular oxygen. Green Chem 2011;13:5547.
[511] Nie J, Liu H. Aerobic oxidation of 5-hydroxymethylfurfural to 2,5- [539] Lan J, Lin J, Chen Z, Yin G. Transformation of 5-hydroxymethylfurfural (HMF)
diformylfuran on supported vanadium oxide catalysts: structural effect and to maleic anhydride by aerobic oxidation with heteropolyacid catalysts. ACS
reaction mechanism. Pure Appl Chem 2012;84:76577. Catal 2015;5:203541.
[512] Nie J, Xie J, Liu H. Ecient aerobic oxidation of 5-hydroxymethylfurfural to [540] Shi S, Guo H, Yin G. Synthesis of maleic acid from renewable resources:
2,5-diformylfuran on supported Ru catalysts. J Catal 2013;301:8391. catalytic oxidation of furfural in liquid media with dioxygen. Catal Commun
[513] Xiang X, He L, Yang Y, Guo B, Tong D, Hu C. A one-pot two-step approach 2011;12:7313.
for the catalytic conversion of glucose into 2,5-diformylfuran. Catal Lett [541] Lan J, Chen Z, Lin J, Yin G. Catalytic aerobic oxidation of renewable furfural
2011;141:73541. to maleic anhydride and furanone derivatives with their mechanistic studies.
[514] Yang ZZ, Deng J, Pan T, Guo QX, Fu Y. A one-pot approach for conversion of Green Chem 2014;16:43518.
fructose to 2,5-diformylfuran by combination of Fe3O4-SBA-SO3H and [542] Alonso-Fagndez N, Granados ML, Mariscal R, Ojeda M. Selective conversion
K-OMS-2. Green Chem 2012;14:29869. of furfural to maleic anhydride and furan with VO x /Al 2 O 3 catalysts.
[515] Takagaki A, Takahashi M, Nishimura S, Ebitani K. One-pot synthesis of ChemSusChem 2012;5:198490.
2,5-diformylfuran from carbohydrate derivatives by sulfonated resin and [543] Alonso-Fagndez N, Agirrezabal-Telleria I, Arias PL, Fierro JLG, Mariscal R,
hydrotalcite-supported ruthenium catalysts. ACS Catal 2011;1:15625. Lpez Granados M. Aqueous-phase catalytic oxidation of furfural with H2O2:
[516] Yadav GD, Sharma RV. Biomass derived chemicals: environmentally benign high yield of maleic acid by using titanium silicalite-1. RSC Adv
process for oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran by 2014;4:5496072.
using nano-brous Ag-OMS-2-catalyst. Appl Catal B: Environ 2014;147:293 [544] Ghaznavi T, Neagoe C, Patience GS. Partial oxidation of D-xylose to maleic
301. anhydride and acrylic acid over vanadyl pyrophosphate. Biomass Bioenergy
[517] Nie J, Xie J, Liu H. Activated carbon-supported ruthenium as an ecient 2014;71:28593.
catalyst for selective aerobic oxidation of 5-hydroxymethylfurfural to [545] Taarning E, Nielsen IS, Egeblad K, Madsen R, Christensen CH. Chemicals from
2,5-diformylfuran. Chin J Catal 2013;34:8715. renewables: aerobic oxidation of furfural and hydroxymethylfurfural over
[518] Jia X, Ma J, Wang M, Du Z, Lu F, Wang F, et al. Promoted role of Cu(NO3)2 on gold catalysts. ChemSusChem 2008;1:758.
aerobic oxidation of 5-hydroxymethylfurfural to 2,5-diformylfuran over [546] Menegazzo F, Fantinel T, Signoretto M, Pinna F, Manzoli M. On the process
VOSO4. Appl Catal A Gen 2014;482:2316. for furfural and HMF oxidative esterication over Au/ZrO 2 . J Catal
[519] Le NT, Lakshmanan P, Cho K, Han Y, Kim H. Selective oxidation of 2014;319:6170.
5-hydroxymethyl-2-furfural into 2,5-diformylfuran over VO2+ and Cu2+ ions [547] Menegazzo F, Signoretto M, Pinna F, Manzoli M, Aina V, Cerrato G, et al.
immobilized on sulfonated carbon catalysts. Appl Catal A Gen 2013;464:305 Oxidative esterication of renewable furfural on gold-based catalysts: which
12. is the best support? J Catal 2014;309:2417.
[520] Wang Y, Liu B, Huang K, Zhang Z. Aerobic oxidation of biomass-derived [548] Menegazzo F, Signoretto M, Marchese D, Pinna F, Manzoli M. Structure
5-(hydroxymethyl) furfural into 2, 5-diformylfuran catalyzed by the trimetallic activity relationships of Au/ZrO2 catalysts for 5-hydroxymethylfurfural
mixed oxide (CoCeRu). Ind Eng Chem Res 2014;53:131319. oxidative esterication: effects of zirconia sulphation on gold dispersion,
[521] Liu R, Chen J, Chen L, Guo Y, Zhong J. One-step approach to 2,5-diformylfuran position and shape. J Catal 2015;326:18.
from fructose by using a bifunctional and recyclable acidic polyoxometalate [549] Podolean I, Kuncser V, Gheorghe N, Macovei D, Parvulescu VI, Coman SM.
catalyst. ChemPlusChem 2014;79:144854. Ru-based magnetic nanoparticles (MNP) for succinic acid synthesis from
[522] Liu Y, Zhu L, Tang J, Liu M, Cheng R, Hu C. One-pot, one-step synthesis of levulinic acid. Green Chem 2013;15:307782.
2,5-diformylfuran from carbohydrates over Mo-containing keggin [550] Choudhary H, Nishimura S, Ebitani K. Metal-free oxidative synthesis of
heteropolyacids. ChemSusChem 2014;7:35417. succinic acid from biomass-derived furan compounds using a solid acid
[523] Nie J, Liu H. Ecient aerobic oxidation of 5-hydroxymethylfurfural to catalyst with hydrogen peroxide. Appl Catal A Gen 2013;458:5562.
2,5-diformylfuran on manganese oxide catalysts. J Catal 2014;316:5766. [551] Wang Y, Vogelgsang F, Romn-Leshkov Y. Acid-catalyzed oxidation of
[524] Chen J, Guo Y, Chen J, Song L, Chen L. One-step approach to 2,5-diformylfuran levulinate derivatives to succinates under mild conditions. ChemCatChem
from fructose by proton- and vanadium-containing graphitic carbon nitride. 2015;7:91620.
ChemCatChem 2014;6:317481. [552] Wu L, Dutta S, Mascal M. Ecient, chemical-catalytic approach to the
[525] Antonyraj CA, Kim B, Kim Y, Shin S, Lee KY, Kim I, et al. Heterogeneous production of 3-hydroxypropanoic acid by oxidation of biomass-derived
selective oxidation of 5-hydroxymethyl-2-furfural (HMF) into 2,5- levulinic acid with hydrogen peroxide. ChemSusChem 2015;8:11679.
diformylfuran catalyzed by vanadium supported activated carbon in MIBK, [553] Dutta S, Wu L, Mascal M. Ecient, metal-free production of succinic acid
extracting solvent for HMF. Catal Commun 2014;57:648. by oxidation of biomass-derived levulinic acid with hydrogen peroxide. Green
[526] Xu F, Zhang Z. Polyaniline-grafted VO(acac)2: an effective catalyst for the Chem 2015;17:23358.
synthesis of 2, 5-diformylfuran from 5-hydroxymethylfurfural and fructose. [554] Gorbanev YY, Kegns S, Riisager A. Selective aerobic oxidation of
ChemCatChem 2015;7:14707. 5-hydroxymethylfurfural in water over solid ruthenium hydroxide catalysts
[527] Sdaba I, Gorbanev YY, Kegns S, Putluru SSR, Berg RW, Riisager A. Catalytic with magnesium-based supports. Catal Lett 2011;141:175260.
performance of zeolite-supported vanadia in the aerobic oxidation of [555] Sthlberg T, Srensen MG, Riisager A. Direct conversion of glucose to
5-hydroxymethylfurfural to 2,5-diformylfuran. ChemCatChem 2013;5:28493. 5-(hydroxymethyl)furfural in ionic liquids with lanthanide catalysts. Green
[528] Kompanets MO, Kushch OV, Litvinov YE, Pliekhov OL, Novikova KV, Chem 2010;12:3215.
Novokhatko AO, et al. Oxidation of 5-hydroxymethylfurfural to [556] Nielsen IS, Taaring E, Egeblad K, Madsen R, Christensen CH. Direct aerobic
2,5-diformylfuran with molecular oxygen in the presence of N- oxidation of primary alcohols to methyl esters catalyzed by a heterogeneous
hydroxyphthalimide. Catal Commun 2014;57:603. gold catalyst. Catal Lett 2007;116:3540.
[529] Tong X, Sun Y, Bai X, Li Y. Highly ecient aerobic oxidation of biomass- [557] Albonetti S, Pasini T, Lolli A, Blosi M, Piccinini M, Dimitratos N, et al. Selective
derived 5-hydroxymethyl furfural to produce 2,5-diformylfuran in the oxidation of 5-hydroxymethyl-2-furfural over TiO2-supported gold-copper
presence of copper salts. RSC Adv 2014;4:4430711. catalysts prepared from preformed nanoparticles: effect of Au/Cu ratio. Catal
[530] Chen J, Zhong J, Guo Y, Chen L. Ruthenium complex immobilized on poly(4- Today 2012;195:1206.
vinylpyridine)-functionalized carbon-nanotube for selective aerobic oxidation [558] Davis SE, Zope BN, Davis RJ. On the mechanism of selective oxidation of
of 5-hydroxymethylfurfural to 2,5-diformylfuran. RSC Adv 2015;5:593340. 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid over supported Pt and
[531] Artz J, Mallmann S, Palkovits R. Selective aerobic oxidation of HMF to Au catalysts. Green Chem 2012;14:1437.
2,5-diformylfuran on covalent triazine frameworks-supported Ru catalysts. [559] Yi G, Teong SP, Li X, Zhang Y. Purication of biomass-derived
ChemSusChem 2015;8:6729. 5-hydroxymethylfurfural and its catalytic conversion to 2,5-furandicarboxylic
[532] Tao F, Cui Y, Yang P, Gong Y. One-pot, one-step, catalytic synthesis of acid. ChemSusChem 2014;7:21315.
2,5-diformylfuran from fructose. Russ J Phys Chem A 2014;88:10916. [560] Yi G, Teong SP, Zhang Y. The direct conversion of sugars into 2,5-
[533] Laugel C, Estrine B, Le Bras J, Hoffmann N, Marinkovic S, Muzart J. NaBr/ furandicarboxylic acid in a triphasic system. ChemSusChem 2015;8:1151
DMSO-induced synthesis of 2,5-diformylfuran from fructose or 5.
5-(hydroxymethyl)furfural. ChemCatChem 2014;6:11958. [561] Amarasekara AS, Green D, McMillan E. Ecient oxidation of 5-
[534] Liu B, Zhang Z, Lv K, Deng K, Duan H. Ecient aerobic oxidation of biomass- hydroxymethylfurfural to 2,5-diformylfuran using Mn(III)-salen catalysts.
derived 5-hydroxymethylfurfural to 2,5-diformylfuran catalyzed by magnetic Catal Commun 2008;9:2868.
nanoparticle supported manganese oxide. Appl Catal A Gen 2014;472:6471. [562] Ziach K, Obrocka-Hrycyna A, Jurczak J. Dynamic combinatorial libraries of
[535] Karimi B, Mirzaei HM, Farhangi E. Fe3O4@SiO2TEMPO as a magnetically 2,5-diformylfuran-derived macrocycles. J Org Chem 2014;79:1033441.
recyclable catalyst for highly selective aerobic oxidation of 5- [563] Ma J, Du Z, Xu J, Chu Q, Pang Y. Ecient aerobic oxidation of
hydroxymethylfurfural into 2,5-diformylfuran under metal- and halogen-free 5-hydroxymethylfurfural to 2,5-diformylfuran, and synthesis of a uorescent
conditions. ChemCatChem 2014;6:75862. material. ChemSusChem 2011;4:514.
184 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

[564] Halliday GA, Young JRJ, Grushin VV. One-pot, two-step, practical catalytic [594] Kamm B. Production of platform chemicals and synthesis gas from biomass.
synthesis of 2,5-diformylfuran from fructose. Org Lett 2003;5:20035. Angew Chem Int Ed 2007;46:50568.
[565] Centi G, Triro F, Ebner JR, Franchetti VM. Mechanistic aspects of maleic [595] Palkovits R, Tajvidi K, Procelewska J, Rinaldi R, Ruppert A. Hydrogenolysis
anhydride synthesis from C4 hydrocarbons over phosphorus vanadium oxide. of cellulose combining mineral acids and hydrogenation catalysts. Green
Chem Rev 1988;88:5580. Chem 2010;12:9728.
[566] Tth B, Varga C, Bartha L. Olenmaleic-anhydride copolymer based [596] Yan N, Zhao C, Luo C, Dyson PJ, Liu H, Kou Y. One-step conversion of cellobiose
additives: a novel approach for compatibilizing blends of waste polyethylene to C6-alcohols using a ruthenium nanocluster catalyst. J Am Chem Soc
and crumb rubber. Waste Manage 2015;38:6571. 2006;128:871415.
[567] Liu D, Zhang X, Zhu L, Wu J, L X. Alternating ring-opening copolymerization [597] Deng W, Liu M, Tan X, Zhang Q, Wang Y. Conversion of cellobiose into sorbitol
of styrene oxide and maleic anhydride using asymmetrical bis-Schiff-base in neutral water medium over carbon nanotube-supported ruthenium
metal(III) catalysts. Catal Sci Technol 2015;5:56271. catalysts. J Catal 2010;271:2232.
[568] Guo H, Yin G. Catalytic aerobic oxidation of renewable furfural with [598] Ran M, Liu Y, Chu W, Liu Z, Borgna A. High dispersion of Ru nanoparticles
phosphomolybdic acid catalyst: an alternative route to maleic acid. J Phys supported on carbon nanotubes synthesized by water-assisted chemical vapor
Chem C 2011;115:1751622. deposition for cellobiose conversion. Catal Commun 2012;27:6972.
[569] Casanova O, Iborra S, Corma A. Biomass into chemicals: one pot-base free [599] Ran M, Liu Y, Chu W, Borgna A. Enhanced conversion of cellobiose to sugar
oxidative esterication of 5-hydroxymethyl-2-furfural into 2,5- alcohols by controlled dispersion of ruthenium nanoparticles inside carbon
dimethylfuroate with gold on nanoparticulated ceria. J Catal 2009;265:109 nanotube channels. Catal Lett 2013;143:113944.
16. [600] Luo C, Wang S, Liu H. Cellulose conversion into polyols catalyzed by reversibly
[570] Pan T, Deng J, Xu Q, Zuo Y, Guo QX, Fu Y. Catalytic conversion of furfural formed acids and supported ruthenium clusters in hot water. Angew Chem
into a 2,5-furandicarboxylic acid-based polyester with total carbon utilization. Int Ed 2007;46:76369.
ChemSusChem 2013;6:4750. [601] Liu QY, Liao YH, Wang TJ, Cai CL, Zhang Q, Tsubaki N, et al. One-pot
[571] Ma J, Pang Y, Wang M, Xu J, Ma H, Nie X. The copolymerization reactivity transformation of cellulose to sugar alcohols over acidic metal phosphates
of diols with 2,5-furandicarboxylic acid for furan-based copolyester materials. combined with Ru/C. Ind Eng Chem Res 2014;53:1265564.
J Mater Chem 2012;22:345761. [602] Han JW, Lee H. Direct conversion of cellulose into sorbitol using dual-
[572] Eerhart AJJE, Faaij APC, Patel MK. Replacing fossil based PET with biobased functionalized catalysts in neutral aqueous solution. Catal Comm
PEF; process analysis, energy and GHG balance. Energy Environ Sci 2012;19:11518.
2012;5:640722. [603] Liu M, Deng W, Zhang Q, Wang Y, Wang Y. Polyoxometalate-supported
[573] Gomes M, Gandini A, Silvestre AJD, Reis B. Synthesis and characterization ruthenium nanoparticles as bifunctional heterogeneous catalysts for the
of poly(2,5-furan dicarboxylate)s based on a variety of diols. J Polym Sci Part conversions of cellobiose and cellulose into sorbitol under mild conditions.
A Polym Chem 2011;49:375968. Chem Commun 2011;47:971719.
[574] Ma J, Wang M, Du Z, Chen C, Gao J, Xu J. Synthesis and properties of furan- [604] Xie X, Han J, Wang H, Zhu X, Liu X, Niu Y, et al. Selective conversion of
based imine-linked porous organic frameworks. Polym Chem 2012;3:23469. microcrystalline cellulose into hexitols over a Ru/[Bmim]3PW12O40 catalyst
[575] Amarasekara AS, Green D, Williams LTD. Renewable resources based under mild conditions. Catal Today 2014;233:706.
polymers: synthesis and characterization of 2,5-diformylfuranurea resin. [605] Negoi A, Triantafyllidis K, Parvulescu VI, Coman SM. The hydrolytic
Eur Polym J 2009;45:5958. hydrogenation of cellulose to sorbitol over M (Ru, Ir, Pd, Rh)-BEA-zeolite
[576] Narayanaswamy R, Ismail IS. Cosmetic potential of Southeast Asian herbs: catalysts. Catal Today 2014;223:1228.
an overview. Phytochem Rev 2015;14:41928. [606] Mishra DK, Dabbawala AA, Park JJ, Jhung SH, Hwang JS. Selective
[577] Markus H, Plomp AJ, Sandberg T, Nieminen V, Bitter JH, Murzin DY. hydrogenation of D-glucose to D-sorbitol over HY zeolite supported
Dehydrogenation of hydroxymatairesinol to oxomatairesinol over carbon ruthenium nanoparticles catalysts. Catal Today 2014;232:99107.
nanobre-supported palladium catalysts. J Mol Catal A Chem 2007;274:429. [607] Xi J, Zhang Y, Xia Q, Liu X, Ren J, Lu G, et al. Direct conversion of cellulose
[578] Simakova OA, Murzina EV, Mki-Arvela P, Leino AR, Campo BC, Kordas K, into sorbitol with high yield by a novel mesoporous niobium phosphate
et al. Oxidative dehydrogenation of a biomass derived lignan supported ruthenium bifunctional catalyst. Appl Catal A Gen 2013;459:52
hydroxymatairesinol over heterogeneous gold catalysts. J Catal 2011;282:54 8.
64. [608] Reyes-Luyanda D, Flores-Cruz J, Morales-Prez PJ, Encarnacin-Gmez LG,
[579] Simakova OA, Smolentseva E, Estrada M, Murzina EV, Beloshapkin S, Willfr Shi F, Voyles PM, et al. Bifunctional materials for the catalytic conversion
SM, et al. From woody biomass extractives to health-promoting substances: of cellulose into soluble renewable biorenery feedstocks. Top Catal
selective oxidation of the lignan hydroxymatairesinol to oxomatairesinol over 2012;55:14861.
Au, Pd, and AuPd heterogeneous catalysts. J Catal 2012;291:95103. [609] Wu Z, Ge S, Ren C, Zhang M, Yip A, Xu C. Selective conversion of cellulose
[580] Lpez M, Simakova OA, Murzina EV, Willfr SM, Prosvirin I, Simakov A, et al. into bulk chemicals over Bronsted acid-promoted ruthenium catalyst: one-pot
Gold particle size effect in biomass-derived lignin hydroxymatairesinol vs. sequential process. Green Chem 2012;14:333643.
oxidation over Au/Al2O3 catalysts. Appl Catal A Gen 2015;504:24855. [610] Liao Y, Liu Q, Wang T, Long J, Ma L, Zhang Q. Zirconium phosphate combined
[581] Ragauskas AJ, Beckham GT, Biddy MJ, Chandra R, Chen F, Davis MF, et al. with Ru/C as a highly ecient catalyst for the direct transformation of
Lignin valorization: improving lignin processing in the biorenery. Science cellulose to C6 alditols. Green Chem 2014;16:330512.
2014;344:1246843. [611] Chen J, Wang S, Huang J, Chen L, Ma L, Huang X. Conversion of cellulose
[582] Kang S, Li X, Fan J, Chang J. Hydrothermal conversion of lignin: a review. and cellobiose into sorbitol catalyzed by ruthenium supported on a
Renew Sust Energy Rev 2013;27:54658. polyoxometalate/metalorganic framework hybrid. ChemSusChem
[583] Zhao Y, Xu Q, Pan T, Zuo Y, Fu Y, Guo QX. Depolymerization of lignin by 2013;6:154555.
catalytic oxidation with aqueous polyoxometalates. Appl Catal A Gen [612] Fukuoka A, Dhepe PL. Catalytic conversion of cellulose into sugar alcohols.
2013;467:5048. Angew Chem Int Ed 2006;45:51613.
[584] Gao P, Li C, Wang H, Wang X, Wang A. Perovskite hollow nanospheres for [613] Park DS, Yun D, Kim TY, Baek J, Yun YS, Yi J. A mesoporous carbon-supported
the catalytic wet air oxidation of lignin. Chin J Catal 2013;34:181115. Pt nanocatalyst for the conversion of lignocellulose to sugar alcohols.
[585] Ma R, Xu Y, Zhang X. Catalytic oxidation of biorenery lignin to value-added ChemSusChem 2013;6:22819.
chemicals to support sustainable biofuel production. ChemSusChem [614] Li J, Liu L, Liu Y, Li M, Zhu Y, Liu H, et al. Direct conversion of cellulose using
2015;8:2451. carbon monoxide and water on a PtMo2C/C catalyst. Energy Environ Sci
[586] Chatel G, Rogers RD. Review: oxidation of lignin using ionic liquids an 2014;7:3938.
innovative strategy to produce renewable chemicals. ACS Sust Chem Eng [615] Rodiansono R, Shimazu S. Effective production of sorbitol and mannitol from
2014;2:32239. sugars catalyzed by Ni nanoparticles supported on aluminium hydroxide.
[587] Chenna NK, Jskelinen AS, Vuorinen T. Rapid and selective catalytic Bull Chem Reac Eng Catal 2013;8:406.
oxidation of hexenuronic acid and lignin in cellulosic bers. Ind Eng Chem [616] Pang J, Wang A, Zheng M, Zhang Y, Huang Y, Chen X, et al. Catalytic
Res 2013;52:177449. conversion of cellulose to hexitols with mesoporous carbon supported
[588] Yoshikawa T, Yagi T, Shinohara S, Fukunaga T, Nakasaka Y, Tago T, et al. Ni-based bimetallic catalysts. Green Chem 2012;14:61417.
Production of phenols from lignin via depolymerization and catalytic cracking. [617] Van de Vyver S, Geboers J, Dusselier M, Schepers H, Vosch T, Zhang L, et al.
Fuel Process Technol 2013;108:6975. Selective bifunctional catalytic conversion of cellulose over reshaped Ni
[589] Toledano A, Serrano L, Labidi J. Organosolv lignin depolymerization with particles at the tip of carbon nanobers. ChemSusChem 2010;3:698701.
different base catalysts. J Chem Technol Biotechnol 2012;87:15939. [618] Van de Vyver S, Geboers J, Schutyser W, Dusselier M, Eloy P, Dornez E, et al.
[590] Climent MJ, Corma A, Iborra S. Conversion of biomass platform molecules Tuning the acid/metal balance of carbon nanober-supported nickel catalysts
into fuel additives and liquid hydrocarbon fuels. Green Chem 2014;16:516 for hydrolytic hydrogenation of cellulose. ChemSusChem 2012;5:1549
47. 58.
[591] Larabi C, Maksoud WA, Szeto KC, Garron A, Arquilliere PP, Walter JJ, et al. [619] Ji N, Zhang T, Zheng M, Wang A, Wang H, Wang X, et al. Direct catalytic
Multifunctional heterogeneous catalyst for one step transformation of conversion of cellulose into ethylene glycol using nickel-promoted tungsten
lignocellulosic biomass into low oxygenated hydrocarbons. Appl Catal A Gen carbide catalysts. Angew Chem Int Ed 2008;47:851013.
2015;495:16272. [620] Pang J, Zheng M, Wang A, Zhang T. Catalytic hydrogenation of corn stalk to
[592] Dhepe PL, Fukuoka A. Cellulose conversion under heterogeneous catalysis. ethylene glycol and 1,2-propylene glycol. Ind Eng Chem Res 2011;50:66018.
ChemSusChem 2008;1:96975. [621] Zhao G, Zheng M, Wang A, Zhang T. Catalytic conversion of cellulose to
[593] Dhepe PL, Fukuoka A. Cracking of cellulose over supported metal catalysts. ethylene glycol over tungsten phosphide catalysts. Chin J Catal 2010;31:928
Catal Surv Asia 2007;11:18691. 32.
H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194 185

[622] Ji N, Zhang T, Zheng M, Wang A, Wang H, Wang X, et al. Catalytic conversion [653] Nagpure AS, Lucas N, Chilukuri SV. Ecient preparation of liquid fuel
of cellulose into ethylene glycol over supported carbide catalysts. Catal Today 2,5-dimethylfuran from biomass-derived 5-hydroxymethylfurfural over
2009;147:7785. RuNaY catalyst. ACS Sust Chem Eng 2015;3:290916.
[623] Zhang Y, Wang A, Zhang T. A new 3D mesoporous carbon replicated from [654] Saha B, Bohn CM, Abu-Omar MM. Zinc-assisted hydrodeoxygenation
commercial silica as a catalyst support for direct conversion of cellulose into of biomass-derived 5-hydroxymethylfurfural to 2,5-dimethylfuran.
ethylene glycol. Chem Commun 2010;46:8624. ChemSusChem 2014;7:3095101.
[624] Tai Z, Zhang J, Wang A, Zheng M, Zhang T. Temperature-controlled phase- [655] Shi J, Wang Y, Yu X, Du W, Hou Z. Production of 2, 5-dimethylfuran from
transfer catalysis for ethylene glycol production from cellulose. Chem 5-hydroxymethylfurfural over reduced graphene oxides supported Pt catalyst
Commun 2012;48:70524. under mild conditions. Fuel 2016;163:749.
[625] Tai Z, Zhang J, Wang A, Pang J, Zheng M, Zhang T. Catalytic conversion of [656] Huang YB, Chen MY, Yan L, Guo QX, Fu Y. Nickel-tungsten carbide catalysts
cellulose to ethylene glycol over a low-cost binary catalyst of raney Ni and for the production of 2,5-dimethylfuran from biomass-derived molecules.
tungstic acid. ChemSusChem 2013;6:6528. ChemSusChem 2014;7:106872.
[626] Liu Y, Luo C, Liu H. Tungsten trioxide promoted selective conversion of [657] Thananatthanachon T, Rauchfuss TB. Ecient production of the liquid fuel
cellulose into propylene glycol and ethylene glycol on a ruthenium catalyst. 2,5-dimethylfuran from fructose using formic acid as a reagent. Angew Chem
Angew Chem Int Ed 2012;51:324953. Int Ed 2010;49:661618.
[627] Zheng M, Wang A, Ji N, Pang J, Wang X, Zhang T. Transition metaltungsten [658] De S, Dutta S, Saha B. One-pot conversions of lignocellulosic and algal biomass
bimetallic catalysts for the conversion of cellulose into ethylene glycol. into liquid fuels. ChemSusChem 2012;5:182633.
ChemSusChem 2010;3:636. [659] Nakagawa Y, Tomishige K. Total hydrogenation of furan derivatives over
[628] Xi J, Ding D, Shao Y, Liu X, Lu G, Wang Y. Production of ethylene glycol and silica-supported Ni-Pd alloy catalyst. Catal Commun 2010;12:1546.
its monoether derivative from cellulose. ACS Sust Chem Eng 2014;2:235562. [660] Alamillo R, Tucker M, Chia M, Pagn-Torres Y, Dumesic J. The selective
[629] Wang H, Zhu L, Peng S, Peng F, Yu H, Yang J. High ecient conversion of hydrogenation of biomass-derived 5-hydroxymethylfurfural using
cellulose to polyols with Ru/CNTs as catalyst. Renew Energy 2012;37:1926. heterogeneous catalysts. Green Chem 2012;14:141319.
[630] Deng W, Tan X, Fang W, Zhang Q, Wang Y. Conversion of cellulose into [661] Cai H, Li C, Wang A, Zhang T. Biomass into chemicals: one-pot production
sorbitol over carbon nanotube-supported ruthenium catalyst. Catal Lett of furan-based diols from carbohydrates via tandem reactions. Catal Today
2009;133:16774. 2014;234:5965.
[631] Hattori H, Shishido T. Molecular hydrogen-originated protonic acid site as [662] Yang Y, Du Z, Ma J, Lu F, Zhang J, Xu J. Biphasic catalytic conversion of fructose
active site on solid acid catalyst. Catal Surv Asia 1997;1:20513. by continuous hydrogenation of HMF over a hydrophobic ruthenium catalyst.
[632] Lonergan WW, Vlachos DG, Chen JG. Correlating extent of PtNi bond ChemSusChem 2014;7:13526.
formation with low-temperature hydrogenation of benzene and 1,3-butadiene [663] Ohyama J, Esaki A, Yamamoto Y, Arai S, Satsuma A. Selective hydrogenation
over supported Pt/Ni bimetallic catalysts. J Catal 2010;271:23950. of 2-hydroxymethyl-5-furfural to 2,5-bis(hydroxymethyl)furan over gold
[633] Mu R, Fu Q, Xu H, Zhang H, Huang Y, Jiang Z, et al. Synergetic effect of surface sub-nano clusters. RSC Adv 2013;3:10336.
and subsurface Ni species at Pt-Ni bimetallic catalysts for CO oxidation. J Am [664] Chatterjee M, Ishizaka T, Kawanami H. Selective hydrogenation of
Chem Soc 2011;133:197886. 5-hydroxymethylfurfural to 2,5-bis-(hydroxymethyl)furan using Pt/MCM-41
[634] Rinaldi R, Porcari ADM, Rocha TC, Cassinelli WH, Ribeiro RU, Bueno JMC, et al. in an aqueous medium: a simple approach. Green Chem 2014;16:47349.
Construction of heterogeneous Ni catalysts from supports and colloidal [665] Yang W, Sen A. One-step catalytic transformation of carbohydrates and
nanoparticlesA challenging puzzle. J Mol Catal A Chem 2009;301:1117. cellulosic biomass to 2,5-dimethyltetrahydrofuran for liquid fuels.
[635] De Jong KP, Geus JW. Carbon nanobers: catalytic synthesis and applications. ChemSusChem 2010;3:597603.
Catal Rev 2000;42:481510. [666] Yepez A, Pineda A, Garcia A, Romero AA, Luque R. Chemical transformations
[636] Rodrguez-Reinoso F. The role of carbon materials in heterogeneous catalysis. of glucose to value added products using Cu-based catalytic systems. Phys
Carbon 1998;36:15975. Chem Chem Phys 2013;15:1216572.
[637] Tajvidi K, Hausoul PJ, Palkovits R. Hydrogenolysis of cellulose over Cu-based [667] Mitra J, Zhou X, Rauchfuss T. Pd/C-catalyzed reactions of HMF:
catalysts Analysis of the reaction network. ChemSusChem 2014;7:131117. decarbonylation, hydrogenation, and hydrogenolysis. Green Chem
[638] Wang A, Zhang T. One-pot conversion of cellulose to ethylene glycol with 2015;17:30713.
multifunctional tungsten-based catalysts. Acc Chem Res 2013;46:137786. [668] Liu F, Audemar M, Vigier KDO, Clacens JM, Campo FD, Jrme F. Combination
[639] Hu L, Lin L, Liu S. Chemoselective hydrogenation of biomass-derived of Pd/C and Amberlyst-15 in a single reactor for the acid/hydrogenating
5-hydroxymethylfurfural into the liquid biofuel 2,5-dimethylfuran. Ind Eng catalytic conversion of carbohydrates to 5-hydroxy-2,5-hexanedione. Green
Chem Res 2014;53:996978. Chem 2014;16:411014.
[640] Dutta S, Mascal M. Novel pathways to 2,5-dimethylfuran via biomass-derived [669] Zhou H, Song J, Meng Q, He Z, Jiang Z, Zhou B, et al. Cooperative catalysis of
5-(chloromethyl)furfural. ChemSusChem 2014;7:302830. Pt/C and acid resin for the production of 2,5-dimethyltetrahydrofuran from
[641] Nagpure AS, Venugopal AK, Lucas N, Manikandan M, Thirumalaiswamy R, biomass derived 2,5-hexanedione under mild conditions. Green Chem
Chilukuri S. Renewable fuels from biomass-derived compounds: ru- 2016;18:2205.
containing hydrotalcites as catalysts for conversion of HMF to 2,5- [670] Jackson MA, Appell M, Blackburn JA. Hydrodeoxygenation of fructose to
dimethylfuran. Catal Sci Technol 2015;5:146372. 2,5-dimethyltetrahydrofuran using a sulfur poisoned Pt/C catalyst. Ind Eng
[642] Qian Y, Zhu L, Wang Y, Lu X. Recent progress in the development of biofuel Chem Res 2015;54:705966.
2,5-dimethylfuran. Renew Sust Energy Rev 2015;41:63346. [671] Schlaf M. Selective deoxygenation of sugar polyols to ,-diols and other
[643] Saha B, Abu-Omar MM. Current technologies, economics, and perspectives oxygen content reduced materials A new challenge to homogeneous ionic
for 2,5-dimethylfuran production from biomass-derived intermediates. hydrogenation and hydrogenolysis catalysis. Dalton Trans 2006;464553.
ChemSusChem 2015;8:113342. [672] Tong X, Ma Y, Li Y. Biomass into chemicals: conversion of sugars to furan
[644] Roman-Leshkov Y, Barrett CJ, Liu ZY, Dumesic JA. Production of dimethylfuran derivatives by catalytic processes. Appl Catal A Gen 2010;385:113.
for liquid fuels from biomass-derived carbohydrates. Nature 2007;447:9825. [673] Kong X, Zhu Y, Zheng H, Dong F, Zhu Y, Li Y-W. Switchable synthesis
[645] Upare PP, Hwang DW, Hwang YK, Lee UH, Hong DY, Chang JS. An integrated of 2,5-dimethylfuran and 2,5-dihydroxymethyltetrahydrofuran from
process for the production of 2,5-dimethylfuran from fructose. Green Chem 5-hydroxymethylfurfural over Raney Ni catalyst. RSC Adv 2014;4:6046772.
2015;17:331013. [674] Kang ES, Chae DW, Kim B, Kim YG. Ecient preparation of DHMF and HMFA
[646] Chidambaram M, Bell AT. A two-step approach for the catalytic conversion from biomass-derived HMF via a Cannizzaro reaction in ionic liquids. J Ind
of glucose to 2,5-dimethylfuran in ionic liquids. Green Chem 2010;12:1253 Eng Chem 2012;18:1747.
62. [675] Dutta S, De S, Saha B. A brief summary of the synthesis of polyester building-
[647] Wang J, Liu X, Hu B, Lu G, Wang Y. Ecient catalytic conversion of block chemicals and biofuels from 5-hydroxymethylfurfural. ChemPlusChem
lignocellulosic biomass into renewable liquid biofuels via furan derivatives. 2012;77:25972.
RSC Adv 2014;4:311017. [676] Grochowski MR, Yang W, Sen A. Mechanistic study of a one-step catalytic
[648] Wang GH, Hilgert J, Richter FH, Wang F, Bongard HJ, Spliethoff B, et al. conversion of fructose to 2,5-dimethyltetrahydrofuran. Chem Eur J
Platinumcobalt bimetallic nanoparticles in hollow carbon nanospheres for 2012;18:1236371.
hydrogenolysis of 5-hydroxymethylfurfural. Nat Mater 2014;13:293300. [677] Luijkx GCA, Huck NPM, van Rantwijk F, Maat L, van Bekkum H. Ether
[649] Zhu Y, Kong X, Zheng H, Ding G, Zhu Y, Li YW. Ecient synthesis of 2,5- formation in the hydrogenolysis of hydroxymethylfurfural over palladium
dihydroxymethylfuran and 2,5-dimethylfuran from 5-hydroxymethylfurfural catalysts in alcoholic solution. Heterocycles 2009;77:103744.
using mineral-derived Cu catalysts as versatile catalysts. Catal Sci Technol [678] Kong X, Zhu Y, Zheng H, Li X, Zhu Y, Li YW. Ni nanoparticles inlaid nickel
2015;5:420817. phyllosilicate as a metal-acid bifunctional catalyst for low-temperature
[650] Yang P, Cui Q, Zu Y, Liu X, Lu G, Wang Y. Catalytic production of 2, hydrogenolysis reactions. ACS Catal 2015;5:591420.
5-dimethylfuran from 5-hydroxymethylfurfural over Ni/Co3O4 catalyst. Catal [679] Panagiotopoulou P, Martin N, Vlachos DG. Liquid-phase catalytic transfer
Commun 2015;66:559. hydrogenation of furfural over homogeneous Lewis acid-Ru/C catalysts.
[651] Nishimura S, Ikeda N, Ebitani K. Selective hydrogenation of biomass-derived ChemSusChem 2015;8:204654.
5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF) under [680] Sharma RV, Das U, Sammynaiken R, Dalai AK. Liquid phase chemo-selective
atmospheric hydrogen pressure over carbon supported PdAu bimetallic catalytic hydrogenation of furfural to furfuryl alcohol. Appl Catal A Gen
catalyst. Catal Today 2014;232:8998. 2013;454:12736.
[652] Zu Y, Yang P, Wang J, Liu X, Ren J, Lu G, et al. Ecient production of the liquid [681] Yan K, Wu G, Laeur T, Jarvis C. Production, properties and catalytic
fuel 2,5-dimethylfuran from 5-hydroxymethylfurfural over Ru/Co3O4 catalyst. hydrogenation of furfural to fuel additives and value-added chemicals. Renew
Appl Catal B: Environ 2014;146:2448. Sust Energy Rev 2014;38:66376.
186 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

[682] Zhang W, Zhu Y, Niu S, Li Y. A study of furfural decarbonylation on K-doped [713] Lessard J, Morin J-F, Wehrung J-F, Magnin D, Chornet E. High yield conversion
Pd/Al2O3 catalysts. J Mol Catal A Chem 2011;335:7181. of residual pentoses into furfural via zeolite catalysis and catalytic
[683] Chuang IS, Maciel GE, Myers GE. Carbon-13 NMR study of curing in furfuryl hydrogenation of furfural to 2-methylfuran. Top Catal 2010;53:12314.
alcohol resins. Macromolecules 1984;17:108790. [714] Panagiotopoulou P, Martin N, Vlachos DG. Effect of hydrogen donor on liquid
[684] Burnette LW. The production of rubber from furfural. Rubber Chem Technol phase catalytic transfer hydrogenation of furfural over a Ru/RuO2/C catalyst.
1945;18:2845. J Mol Catal A Chem 2014;392:2238.
[685] Luo W, Liu J, Ma Y, Zhang B, Yang W. Preparation of polymer nanoparticles [715] Aliaga C, Tsung CK, Alayoglu S, Komvopoulos K, Yang P, Somorjai GA. Sum
from renewable biobased furfuryl alcohol and maleic anhydride by stabilizer- frequency generation vibrational spectroscopy and kinetic study of
free dispersion polymerization. J Polym Sci Part A Polym Chem 2-methylfuran and 2,5-dimethylfuran hydrogenation over 7 nm platinum
2012;50:360617. cubic nanoparticles. J Phys Chem C 2011;115:81049.
[686] Fam A, Eldridge A, Misra M. Mechanical characteristics of glass bre reinforced [716] Biradar NS, Hengne AA, Birajdar SN, Swami R, Rode CV. Tailoring the product
polymer made of furfuryl alcohol bio-resin. Mater Struct 2014;47:1195204. distribution with batch and continuous process options in catalytic
[687] Lange J-P, van de Graaf WD, Haan RJ. Conversion of furfuryl alcohol into ethyl hydrogenation of furfural. Org Process Res Dev 2014;18:143442.
levulinate using solid acid catalysts. ChemSusChem 2009;2:43741. [717] Mizugaki T, Togo K, Maeno Z, Mitsudome T, Jitsukawa K, Kaneda K. One-pot
[688] Yao J, Wang H. Preparation of crystalline mesoporous titania using furfuryl transformation of levulinic acid to 2-methyltetrahydrofuran catalyzed by
alcohol as polymerizable solvent. Ind Eng Chem Res 2007;46:62648. Pt-Mo/H-beta in water. ACS Sust Chem Eng 2016;4:6825.
[689] Dunlop AP, Peters JFN. The nature of furfuryl alcohol. Ind Eng Chem [718] Sitthisa S, Pham T, Prasomsri T, Sooknoi T, Mallinson RG, Resasco DE.
1942;34:81417. Conversion of furfural and 2-methylpentanal on Pd/SiO2 and Pd-Cu/SiO2
[690] Rao R, Dandekar A, Baker RTK, Vannice MA. Properties of copper chromite catalysts. J Catal 2011;280:1727.
catalysts in hydrogenation reactions. J Catal 1997;171:40619. [719] Nagaraja BM, Siva Kumar V, Shasikala V, Padmasri AH, Sreedhar B, David Raju
[691] Nagaraja BM, Padmasri AH, Seetharamulu P, Hari Prasad Reddy K, David Raju B, et al. A highly ecient Cu/MgO catalyst for vapour phase hydrogenation
B, Rama Rao KS. A highly active Cu-MgO-Cr2O3 catalyst for simultaneous of furfural to furfuryl alcohol. Catal Commun 2003;4:28793.
synthesis of furfuryl alcohol and cyclohexanone by a novel coupling route [720] Rao RS, Baker RTK, Vannice MA. Furfural hydrogenation over carbon-
Combination of furfural hydrogenation and cyclohexanol dehydrogenation. supported copper. Catal Lett 1999;60:517.
J Mol Catal A Chem 2007;278:2937. [721] Luo H, Li H, Zhuang L. Furfural hydrogenation to furfuryl alcohol over a novel
[692] Yan K, Liao J, Wu X, Xie X. A noble-metal free Cu-catalyst derived from Ni-Co-B amorphous alloy catalyst. Chem Lett 2001;5:4045.
hydrotalcite for highly ecient hydrogenation of biomass-derived furfural [722] Lee S-P, Chen Y-W. Selective hydrogenation of furfural on Ni-P, Ni-B, and
and levulinic acid. RSC Adv 2013;3:38536. Ni-P-B ultrane materials. Ind Eng Chem Res 1999;38:254856.
[693] Nagaraja BM, Padmasri AH, David Raju B, Rama Rao KS. Vapor phase selective [723] Gowda AS, Parkin S, Ladipo FT. Hydrogenation and hydrogenolysis of furfural
hydrogenation of furfural to furfuryl alcohol over Cu-MgO coprecipitated and furfuryl alcohol catalyzed by ruthenium(II) bis(diimine) complexes. Appl
catalysts. J Mol Catal A Chem 2007;265:907. Organometal Chem 2012;26:8693.
[694] Xu C, Zheng L, Liu J, Huang Z. Furfural hydrogenation on nickel-promoted [724] Vorotnikov V, Mpourmpakis G, Vlachos DG. DFT study of furfural conversion
Cu-containing catalysts prepared from hydrotalcite-like precursors. Chin J to furan, furfuryl alcohol, and 2-methylfuran on Pd(111). ACS Catal
Chem 2011;29:6917. 2012;2:2496504.
[695] Chen X, Li H, Luo H, Qiao M. Liquid phase hydrogenation of furfural to furfuryl [725] Merat N, Godawa C, Gaset A. High selective production of tetrahydrofurfuryl
alcohol over Mo-doped Co-B amorphous alloy catalysts. Appl Catal A Gen alcohol: catalytic hydrogenation of furfural and furfuryl alcohol. J Chem
2002;233:1320. Technol Biotechnol 1990;48:14559.
[696] Li H, Luo H, Zhuang L, Dai W, Qiao M. Liquid phase hydrogenation of furfural [726] Khan F-A, Vallat A, Sss-Fink G. Highly selective low-temperature
to furfuryl alcohol over the Fe-promoted Ni-B amorphous alloy catalysts. J hydrogenation of furfuryl alcohol to tetrahydrofurfuryl alcohol catalysed by
Mol Catal A Chem 2003;203:26775. hectorite-supported ruthenium nanoparticles. Catal Commun 2011;12:1428
[697] Li H, Zhang S, Luo H. A Ce-promoted Ni-B amorphous alloy catalyst (NiCeB) 31.
for liquid-phase furfural hydrogenation to furfural alcohol. Mater Lett [727] Tike MA, Mahajani VV. Kinetics of liquid-phase hydrogenation of furfuryl
2004;58:27416. alcohol to tetrahydrofurfuryl alcohol over a Ru/TiO2 catalyst. Ind Eng Chem
[698] Li H, Chai W-M, Luo H-S, Li H-X. Hydrogenation of furfural to furfuryl alcohol Res 2007;46:327582.
over Co-B amorphous catalysts prepared by chemical reduction in variable [728] Seo G, Chon H. Hydrogenation of furfural over copper-containing catalysts.
media. Chin J Chem 2006;24:17048. J Catal 1981;67:4249.
[699] Vaidya PD, Mahajani VV. Kinetics of liquid-phase hydrogenation of [729] Zhu YL, Xiang HW, Li YW, Jiao HJ, Wu GS, Zhong B, et al. A new strategy for
furfuraldehyde to furfuryl alcohol over a Pt/C catalyst. Ind Eng Chem Res the ecient synthesis of 2-methylfuran and -butyrolactone. New J Chem
2003;42:38815. 2003;27:20810.
[700] Kijenski J, Winiarek P, Paryjczak T, Lewicki A, Mikoajska A. Platinum [730] Zheng HY, Yang J, Zhu YL, Zhao GW. Synthesis of -butyrolactone and
deposited on monolayer supports in selective hydrogenation of furfural to 2-methylfuran through the coupling of dehydrogenation and hydrogenation
furfuryl alcohol. Appl Catal A Gen 2002;233:17182. over copper-chromite catalyst. React Kinet Catal Lett 2004;82:2639.
[701] Merlo AB, Vetere V, Ruggera JF, Casella ML. Bimetallic PtSn catalyst for the [731] Yang J, Zheng HY, Zhu YL, Zhao GW, Zhang CH, Teng BT, et al. Effects of
selective hydrogenation of furfural to furfuryl alcohol in liquid-phase. Catal calcination temperature on performance of Cu-Zn-Al catalyst for synthesizing
Commun 2009;10:16659. -butyrolactone and 2-methylfuran through the coupling of dehydrogenation
[702] Wei S, Cui H, Wang J, Zhuo S, Yi W, Wang L, et al. Preparation and activity and hydrogenation. Catal Commun 2004;5:50510.
evaluation of NiMoB/-Al2O3 catalyst by liquid-phase furfural hydrogenation. [732] Dong F, Zhu Y, Zheng H, Zhu Y, Li X, Li Y. Cr-free Cu-catalysts for the selective
China Particuol 2011;9:6974. hydrogenation of biomass-derived furfural to 2-methylfuran: the synergistic
[703] Wu J, Shen Y, Liu C, Wang H, Geng C, Zhang Z. Vapor phase hydrogenation effect of metal and acid sites. J Mol Catal A Chem 2015;398:1408.
of furfural to furfuryl alcohol over environmentally friendly CuCa/SiO2 [733] Sitthisa S, Sooknoi T, Ma Y, Balbuena PB, Resasco DE. Kinetics and mechanism
catalyst. Catal Commun 2005;6:6337. of hydrogenation of furfural on Cu/SiO2 catalysts. J Catal 2011;277:113.
[704] Sitthisa S, Resasco DE. Hydrodeoxygenation of furfural over supported metal [734] Shanmuganathan S, Natalia D, van den Wittenboer A, Kohlmann C,
catalysts: a comparative study of Cu, Pd and Ni. Catal Lett 2011;141:78491. Greiner L, de Mara PD. Enzyme-catalyzed CC bond formation using
[705] Mironenko RM, Belskaya OB, Gulyaeva TI, Nizovskii AI, Kalinkin AV, 2-methyltetrahydrofuran (2-MTHF) as (co)solvent: ecient and bio-based
Bukhtiyarov VI, et al. Effect of the nature of carbon support on the formation alternative to DMSO and MTBE. Green Chem 2010;12:22405.
of active sites in Pd/C and Ru/C catalysts for hydrogenation of furfural. Catal [735] Pace V, Hoyos P, Fernndez M, Sinisterra JV, Alcntara AR.
Today 2015;249:14552. 2-Methyltetrahydrofuran as a suitable green solvent for phthalimide
[706] Perez RF, Fraga MA. Hemicellulose-derived chemicals: one-step production functionalization promoted by supported KF. Green Chem 2010;12:1380
of furfuryl alcohol from xylose. Green Chem 2014;16:394250. 2.
[707] Nakagawa Y, Nakazawa H, Watanabe H, Tomishige K. Total hydrogenation [736] Pace V, Alcntarab AR, Holzera W. Highly ecient chemoselective N-TBS
of furfural over a silica-supported nickel catalyst prepared by the reduction protection of anilines under exceptional mild conditions in the eco-friendly
of a nickel nitrate precursor. ChemCatChem 2012;4:17917. solvent 2-methyltetrahydrofuran. Green Chem 2011;13:19869.
[708] Khairi S, Hara T, Ichikunia N, Shimazu S. Highly ecient and selective [737] Cho A, Shin J, Takagaki A, Kikuchi R, Oyama ST. Ligand and ensemble effects
hydrogenation of unsaturated carbonyl compounds using Ni-Sn alloy in bimetallic NiFe phosphide catalysts for the hydrodeoxygenation of
catalysts. Catal Sci Technol 2012;2:213945. 2-methyltetrahydrofuran. Top Catal 2012;55:96980.
[709] Ordomsky VV, Schouten JC, van der Schaaf J, Nijhuis TA. Biphasic single- [738] Huber GW, Iborra S, Corma A. Synthesis of transportation fuels from biomass:
reactor process for dehydration of xylose and hydrogenation of produced chemistry, catalysts, and engineering. Chem Rev 2006;106:404498.
furfural. Appl Catal A Gen 2013;451:613. [739] Liu X, nalw B, Jensen KF. Heterogeneous catalysis with continuous ow
[710] Zheng HY, Zhu YL, Teng BT, Bai ZQ, Zhang CH, Xiang HW, et al. Towards microreactors. Catal Sci Technol 2012;2:21348.
understanding the reaction pathway in vapour phase hydrogenation of [740] Fegyverneki D, Orha L, Lng G, Horvth IT. Gamma-valerolactone-based
furfural to 2-methylfuran. J Mol Catal A Chem 2006;246:1823. solvents. Tetrahedron 2010;66:107881.
[711] Sitthisa S, An W, Resasco DE. Selective conversion of furfural to methylfuran [741] Duan ZQ, Hu F. Highly ecient synthesis of phosphatidylserine in the
over silica-supported Ni-Fe bimetallic catalysts. J Catal 2011;284:90101. eco-friendly solvent -valerolactone. Green Chem 2012;14:15813.
[712] Lee WS, Wang Z, Zheng W, Vlachos DG, Bhan A. Vapor phase [742] Luterbacher JS, Rand JM, Alonso DM, Han J, Youngquist JT, Maravelias CT,
hydrodeoxygenation of furfural to 2-methylfuran on molybdenum carbide et al. Nonenzymatic sugar production from biomass using biomass-derived
catalysts. Catal Sci Technol 2014;4:234052. -valerolactone. Science 2014;343:27780.
H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194 187

[743] Yan K, Yang Y, Chai J, Lu Y. Catalytic reactions of gamma-valerolactone: a [773] Li W, Xie J-H, Lin H, Zhou QL. Highly ecient hydrogenation of biomass-
platform to fuels and value-added chemicals. Appl Catal B: Environ derived levulinic acid to -valerolactone catalyzed by iridium pincer
2015;179:292304. complexes. Green Chem 2012;14:238890.
[744] Caretto A, No M, Selva M, Perosa A. Upgrading of biobased lactones with [774] Testa ML, Corbel-Demailly L, Parola VL, Venezia AM, Pinel C. Effect of Au on
dialkylcarbonates. ACS Sust Chem Eng 2014;2:213141. Pd supported over HMS and Ti doped HMS as catalysts for the hydrogenation
[745] Derle SN, Parikh PA. Hydrogenation of levulinic acid and -valerolactone: steps of levulinic acid to -valerolactone. Catal Today 2015;257:2916.
towards biofuels. Biomass Conv Bioref 2014;4:2939. [775] Yan K, Laeur T, Liao J. Facile synthesis of palladium nanoparticles supported
[746] Wright WRH, Palkovits R. Development of heterogeneous catalysts for the on multi-walled carbon nanotube for ecient hydrogenation of biomass-
conversion of levulinic acid to -valerolactone. ChemSusChem 2012;5:1657 derived levulinic acid. Nanopart Res 2013;15:190612.
67. [776] Yan K, Laeur T, Wu G, Liao J, Ceng C, Xie X. Highly selective production of
[747] Horvth IT, Mehdi H, Fbos V, Boda L, Mika LT. -Valerolactone A sustainable value-added -valerolactone from biomass-derived levulinic acid using the
liquid for energy and carbon-based chemicals. Green Chem 2008;10:238 robust Pd nanoparticles. Appl Catal A Gen 2013;468:528.
42. [777] Shimizu K, Kanno S, Kon K. Hydrogenation of levulinic acid to -valerolactone
[748] Bond JQ, Alonso DM, Wang D, West RM, Dumesic JA. Integrated catalytic by Ni and MoOx co-loaded carbon catalysts. Green Chem 2014;16:3899903.
conversion of -valerolactone to liquid alkenes for transportation fuels. [778] Mohan V, Venkateshwarlu V, Pramod CV, Raju BD, Rao KSR. Vapour phase
Science 2010;327:111014. hydrocyclisation of levulinic acid to -valerolactone over supported Ni
[749] Alonso DM, Wettstein SG, Dumesic JA. Gamma-valerolactone, a sustainable catalysts. Catal Sci Technol 2014;4:12539.
platform molecule derived from lignocellulosic biomass. Green Chem [779] Rong Z, Sun Z, Wang L, Lv J, Wang Y, Wang Y. Ecient conversion of levulinic
2013;15:58495. acid into -valerolactone over Raney Ni catalyst prepared from melt-
[750] Abdelrahman OA, Heyden A, Bond JQ. Analysis of kinetics and reaction quenching alloy. Catal Lett 2014;144:176671.
pathways in the aqueous-phase hydrogenation of levulinic acid to form [780] Putrakumar B, Nagaraju N, Kumar VP, Chary KVR. Hydrogenation of levulinic
-valerolactone over Ru/C. ACS Catal 2014;4:117181. acid to -valerolactone over copper catalysts supported on -Al2O3. Catal
[751] Serrano-Ruiz JC, West RM, Durnesic JA. Catalytic conversion of renewable Today 2015;250:20917.
biomass resources to fuels and chemicals. Annu Rev Chem Biomol Eng [781] Yan K, Chen A. Ecient hydrogenation of biomass-derived furfural and
2010;1:79100. levulinic acid on the facilely synthesized noble-metal-free Cu-Cr catalyst.
[752] Zhang J, Wu S, Li B, Zhang HD. Advances in the catalytic production of Energy 2013;58:35763.
valuable levulinic acid derivatives. ChemCatChem 2012;4:12307. [782] Balla P, Perupogu V, Vanama PK, Komandur VRC. Hydrogenation of biomass-
[753] Van de Vyver S, Thomas J, Geboers J, Keyzer S, Smet M, Dehaen W, et al. derived levulinic acid to -valerolactone over copper catalysts supported on
Catalytic production of levulinic acid from cellulose and other biomass- ZrO2. J Chem Technol Biotechnol 2015;91:76976.
derived carbohydrates with sulfonated hyperbranched poly(arylene [783] Park JY, Kim MA, Lee SJ, Jung J, Jang HM, Upare PP, et al. Preparation and
oxindole)s. Energy Environ Sci 2011;4:360110. characterization of carbon-encapsulated iron nanoparticles and their catalytic
[754] Weingarten R, Conner WC, Huber GW. Production of levulinic acid from activity in the hydrogenation of levulinic acid. J Mater Sci 2015;50:33443.
cellulose by hydrothermal decomposition combined with aqueous phase [784] Zhou H, Song J, Fan H, Zhang B, Yang Y, Hu J, et al. Cobalt catalysts: very
dehydration with a solid acid catalyst. Energy Environ Sci 2012;5:7559 ecient for hydrogenation of biomass-derived ethyl levulinate to gamma-
74. valerolactone under mild conditions. Green Chem 2014;16:38705.
[755] Tominaga K, Mori A, Fukushima Y, Shimada S, Sato K. Mixed-acid systems [785] Heeres H, Handana R, Chunai D, Rasrendra CB, Girisuta B, Heeres HJ.
for the catalytic synthesis of methyl levulinate from cellulose. Green Chem Combined dehydration/(transfer)-hydrogenation of C6-sugars (D-glucose and
2011;13:81012. D-fructose) to -valerolactone using ruthenium catalysts. Green Chem
[756] Rackemann DW, Doherty WOS. The conversion of lignocellulosics to levulinic 2009;11:124755.
acid. Biofuels Bioprod Bioref 2011;5:198214. [786] Ding D, Wang J, Xi J, Liu X, Lu G, Wang Y. High-yield production of levulinic
[757] Runge T, Zhang C. Two-stage acid-catalyzed conversion of carbohydrates into acid from cellulose and its upgrading to -valerolactone. Green Chem
levulinic acid. Ind Eng Chem Res 2012;51:326570. 2014;16:384653.
[758] Maldonado GMG, Assary RS, Dumesic J, Curtiss LA. Experimental and [787] Molinari V, Antonietti M, Esposito D. An integrated strategy for the conversion
theoretical studies of the acid-catalyzed conversion of furfuryl alcohol to of cellulosic biomass into -valerolactone. Catal Sci Technol 2014;4:3626
levulinic acid in aqueous solution. Energy Environ Sci 2012;5:69819. 30.
[759] Hu X, Song Y, Wu L, Gholizadeh M, Li C-Z. One-pot synthesis of levulinic [788] Raspolli Galletti AM, Antonetti C, Ribechini E, Colombini MP, o Di Nasso NN,
acid/ester from C5 carbohydrates in a methanol medium. ACS Sust Chem Eng Bonari E. From giant reed to levulinic acid and gamma-valerolactone: a high
2013;1:15939. yield catalytic route to valeric biofuels. Appl Energy 2013;102:15762.
[760] Cai H, Li C, Wang A, Xu G, Zhang T. Zeolite-promoted hydrolysis of cellulose [789] Hengne AM, Kamble SB, Rode CV. Single pot conversion of furfuryl alcohol
in ionic liquid, insight into the mutual behavior of zeolite, cellulose and ionic to levulinic esters and -valerolactone in the presence of sulfonic acid
liquid. Appl Catal B: Environ 2012;123-4:3338. functionalized ILs and metal catalysts. Green Chem 2013;15:25407.
[761] Chamnankid B, Ratanatawanate C, Faungnawakij K. Conversion of xylose to [790] Chia M, Dumesic JA. Liquid-phase catalytic transfer hydrogenation and
levulinic acid over modied acid functions of alkaline-treated zeolite Y in cyclization of levulinic acid and its esters to -valerolactone over metal oxide
hot-compressed water. Chem Eng J 2014;258:3417. catalysts. Chem Commun 2011;47:122335.
[762] Hengne AM, Rode CV. Cu-ZrO 2 nanocomposite catalyst for selective [791] Tang X, Chen H, Hu L, Hao W, Sun Y, Zeng X, et al. Conversion of biomass
hydrogenation of levulinic acid and its ester to -valerolactone. Green Chem to -valerolactone by catalytic transfer hydrogenation of ethyl levulinate over
2012;14:106472. metal hydroxides. Appl Catal B: Environ 2014;147:82734.
[763] Tang X, Zeng X, Li Z, Hu L, Sun Y, Liu S, et al. Production of -valerolactone [792] Tang X, Hu L, Sun Y, Zhao G, Hao W, Lin L. Conversion of biomass-derived
from lignocellulosic biomass for sustainable fuels and chemicals supply. ethyl levulinate into -valerolactone via hydrogen transfer from supercritical
Renew Sust Energy Rev 2014;40:60820. ethanol over a ZrO2 catalyst. RSC Adv 2013;3:1027784.
[764] Upare PP, Lee JM, Hwang DW, Halligudi SB, Hwang YK, Chang JS. Selective [793] Song J, Wu L, Zhou B, Zhou H, Fan H, Yang Y, et al. A new porous Zr-containing
hydrogenation of levulinic acid to -valerolactone over carbon-supported catalyst with a phenate group: an ecient catalyst for the catalytic transfer
noble metal catalysts. J Ind Eng Chem 2011;17:28792. hydrogenation of ethyl levulinate to -valerolactone. Green Chem
[765] Yan Z, Lin L, Liu S. Synthesis of -valerolactone by hydrogenation of biomass- 2015;17:162632.
derived levulinic acid over Ru/C catalyst. Energy Fuel 2009;23:38538. [794] Wang J, Jaenicke S, Chuah GK. ZirconiumBeta zeolite as a robust catalyst
[766] Sudhakar M, Lakshmi Kantam M, Jaya VS, Kishore R, Ramanujachary KV, for the transformation of levulinic acid to -valerolactone via Meerwein
Venugopal A. Hydroxyapatite as a novel support for Ru in the hydrogenation PonndorfVerley reduction. RSC Adv 2014;4:134819.
of levulinic acid to -valerolactone. Catal Commun 2014;50:1014. [795] Yang Z, Huang YB, Guo QX, Fu Y. RANEY Ni catalyzed transfer hydrogenation
[767] Moreno-Marrodan C, Barbaro P. Energy ecient continuous production of of levulinate esters to -valerolactone at room temperature. Chem Commun
-valerolactone by bifunctional metal/acid catalysis in one pot. Green Chem 2013;49:532830.
2014;16:34348. [796] Geboers J, Wang X, de Carvalho AB, Rinaldi R. Densication of biorenery
[768] Al-Shaal MG, Wright WRH, Palkovits R. Exploring the ruthenium catalysed schemes by H-transfer with Raney Ni and 2-propanol: a case study of
synthesis of -valerolactone in alcohols and utilisation of mild solvent-free a potential avenue for valorization of alkyllevulinates to alkyl -
reaction conditions. Green Chem 2012;14:12603. hydroxypentanoates and -valerolactone. J Mol Catal A Chem 2014;388-
[769] Yao Y, Wang Z, Zhao S, Wang D, Wu Z, Zhang M. A stable and effective 9:10615.
Ru/polyethersulfone catalyst for levulinic acid hydrogenation to [797] Amarasekara AS, Hasan MA. Pd/C catalyzed conversion of levulinic acid to
-valerolactone in aqueous solution. Catal Today 2014;234:24550. -valerolactone using alcohol as a hydrogen donor under microwave
[770] Raspolli Galletti AM, Antonetti C, De Luise V, Martinelli M. A sustainable conditions. Catal Commun 2015;60:57.
process for the production of -valerolactone by hydrogenation of biomass- [798] Deng L, Zhao Y, Li J, Fu Y, Liao B, Guo QX. Conversion of levulinic acid and
derived levulinic acid. Green Chem 2012;14:68894. formic acid into -valerolactone over heterogeneous catalysts. ChemSusChem
[771] Du X, Liu Y, Wang J, Cao Y, Fan K. Catalytic conversion of biomass-derived 2010;3:11725.
levulinic acid into -valerolactone using iridium nanoparticles supported on [799] Fbos V, Mika LT, Horvth IT. Selective conversion of levulinic and formic
carbon nanotubes. Chin J Catal 2013;34:9931001. acids to -valerolactone with the Shvo catalyst. Organometallics
[772] Deng J, Wang Y, Pan T, Xu Q, Guo QX, Fu Y. Conversion of carbohydrate 2014;33:1817.
biomass to -valerolactone by using water-soluble and reusable iridium [800] Ortiz-Cervantes C, Garca JJ. Hydrogenation of levulinic acid to -valerolactone
complexes in acidic aqueous media. ChemSusChem 2013;6:11637. using ruthenium nanoparticles. Inorg Chim Acta 2013;397:1248.
188 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

[801] Du XL, He L, Zhao S, Liu YM, Cao Y, He HY, et al. Hydrogen-independent [829] Wang D, Hakim SH, Alonso DM, Dumesic JA. A highly selective route to linear
reductive transformation of carbohydrate biomass into -valerolactone and alpha olens from biomass-derived lactones and unsaturated acids. Chem
pyrrolidone derivatives with supported gold catalysts. Angew Chem Commun 2013;49:70402.
2011;123:79615. [830] Kellicutt AB, Salary R, Abdelrahman OA, Bond JQ. An examination of the
[802] Du XL, Bi QY, Liu YM, Cao Y, Fan KN. Conversion of biomass-derived levulinate intrinsic activity and stability of various solid acids during the catalytic
and formate esters into -valerolactone over supported gold catalysts. decarboxylation of -valerolactone. Catal Sci Technol 2014;4:2267
ChemSusChem 2011;4:183843. 9.
[803] Yuan J, Li SS, Yu L, Liu YM, Cao Y, He HY, et al. Copper-based catalysts for [831] Grbz EI, Alonso DM, Bond JQ, Dumesic JA. Reactive extraction of levulinate
the ecient conversion of carbohydrate biomass into -valerolactone in the esters and conversion to -valerolactone for production of liquid fuels.
absence of externally added hydrogen. Energy Environ Sci 2013;6:3308 ChemSusChem 2011;4:35761.
13. [832] Han J, Sen SM, Alonso DM, Dumesic JA, Maravelias CT. A strategy for the
[804] Deng L, Li J, Lai DM, Fu Y, Guo QX. Catalytic conversion of biomass-derived simultaneous catalytic conversion of hemicellulose and cellulose from
carbohydrates into -valerolactone without using an external H2 supply. lignocellulosic biomass to liquid transportation fuels. Green Chem
Angew Chem Int Ed 2009;48:652932. 2014;16:65361.
[805] Amarasekara AS, Wiredu B, Edwards DLN. -Valerolactone from pyrolysis of [833] Buitrago-Sierra R, Serrano-Ruiz JC, Rodrguez-Reinoso F, Seplveda-Escribano
calcium salts of levulinic-formic acid mixtures derived from cellulose. A, Dumesic JA. Ce promoted PdNb catalysts for -valerolactone ring-opening
Biomass Bioenergy 2015;72:3944. and hydrogenation. Green Chem 2012;14:331824.
[806] Qi L, Horvth IT. Catalytic conversion of fructose to -valerolactone in [834] Pham HN, Pagan-Torres YJ, Serrano-Ruiz JC, Wang D, Dumesic JA, Datye AK.
-valerolactone. ACS Catal 2012;2:22479. Improved hydrothermal stability of niobia-supported Pd catalysts. Appl Catal
[807] Alonso DM, Gallo JMR, Mellmer MA, Wettstein SG, Dumesic JA. Direct A Gen 2011;397:15362.
conversion of cellulose to levulinic acid and gamma-valerolactone using solid [835] Sun P, Gao G, Zhao Z, Xia C, Li F. Stabilization of cobalt catalysts by
acid catalysts. Catal Sci Technol 2013;3:92731. embedment for ecient production of valeric biofuel. ACS Catal
[808] Wettstein SG, Alonso DM, Chong Y, Dumesic JA. Production of levulinic acid 2014;4:413642.
and gamma-valerolactone (GVL) from cellulose using GVL as a solvent in [836] Palkovits R. Pentenoic acid pathways for cellulosic biofuels. Angew Chem
biphasic systems. Energy Environ Sci 2012;5:8199203. Int Ed 2010;49:43368.
[809] Bui L, Luo H, Gunther WR, Romn-Leshkov Y. Domino reaction catalyzed by [837] Lange JP, Price R, Ayoub P, Louis J, Petrus L, Clarke L, et al. Valeric biofuels:
zeolites with Bronsted and Lewis acid sites for the production of a platform of cellulosic transportation fuels. Angew Chem Int Ed
-valerolactone from furfural. Angew Chem 2013;125:81803. 2010;49:447983.
[810] Alonso DM, Wettstein SG, Mellmer MA, Gurbuz EI, Dumesic JA. Integrated [838] Kon K, Onodera W, Shimizu K. Selective hydrogenation of levulinic acid to
conversion of hemicellulose and cellulose from lignocellulosic biomass. valeric acid and valeric biofuels by a Pt/HMFI catalyst. Catal Sci Technol
Energy Environ Sci 2013;6:7680. 2014;4:322734.
[811] Luo HY, Consoli DF, Gunther WR, Romn-Leshkov Y. Investigation of the [839] Luo W, Deka U, Beale AM, van Eck ERH, Bruijnincx PCA, Weckhuysen BM.
reaction kinetics of isolated Lewis acid sites in Beta zeolites for the Ruthenium-catalyzed hydrogenation of levulinic acid: inuence of the
MeerweinPonndorfVerley reduction of methyl levulinate to -valerolactone. support and solvent on catalyst selectivity and stability. J Catal
J Catal 2014;320:198207. 2013;301:17586.
[812] Li H, Fang Z, Yang S. Direct conversion of sugars and ethyl levulinate into [840] Pan T, Deng J, Xu Q, Xu Y, Guo QX, Fu Y. Catalytic conversion of biomass-
-valerolactone with superparamagnetic acidbase bifunctional ZrFeOx derived levulinic acid to valerate esters as oxygenated fuels using supported
nanocatalysts. ACS Sust Chem Eng 2015;4:23646. ruthenium catalysts. Green Chem 2013;15:296774.
[813] Li H, Fang Z, Yang S. Direct catalytic transformation of biomass derivatives [841] Chan-Thaw CE, Marelli M, Psaro R, Ravasio N, Zaccheria F. New generation
into biofuel component -valerolactone with magnetic nickel-zirconium biofuels: -valerolactone into valeric esters in one pot. RSC Adv 2013;3:1302
nanoparticles. ChemPlusChem 2016;81:13542. 6.
[814] He J, Li H, Lu YM, Liu YX, Wu ZB, Hu DY, et al. Cascade catalytic transfer [842] Scotti N, Dangate M, Gervasini A, Evangelisti C, Ravasio N, Zaccheria F.
hydrogenationcyclization of ethyl levulinate to -valerolactone with AlZr Unraveling the role of low coordination sites in a Cu metal nanoparticle: a
mixed oxides. Appl Catal A Gen 2016;510:1119. step toward the selective synthesis of second generation biofuels. ACS Catal
[815] Ortiz-Cervantes C, Flores-Alamo M, Garca JJ. Hydrogenation of biomass- 2014;4:281826.
derived levulinic acid into -valerolactone catalyzed by palladium complexes. [843] Renz M. Ketonization of carboxylic acids by decarboxylation: mechanism and
ACS Catal 2015;5:142431. scope. Eur J Org Chem 2005;2005:97988.
[816] Xiao C, Goh TW, Qi Z, Goes S, Brashler K, Perez C, et al. Conversion of levulinic [844] Alonso DM, Bond JQ, Serrano-Ruiz JC, Dumesic JA. Production of liquid
acid to gamma-valerolactone over few-layer graphene-supported ruthenium hydrocarbon transportation fuels by oligomerization of biomass-derived C9
catalysts. ACS Catal 2016;6:5939. alkenes. Green Chem 2010;12:9929.
[817] Selva M, Gottardo M, Perosa A. Upgrade of biomass-derived levulinic acid [845] Serrano-Ruiz JC, Wang D, Dumesic JA. Catalytic upgrading of levulinic acid
via Ru/C-catalyzed hydrogenation to -valerolactone in aqueous-organic-ionic to 5-nonanone. Green Chem 2010;12:5747.
liquids multiphase systems. ACS Sust Chem Eng 2013;1:1809. [846] Serrano-Ruiz JC, Braden DJ, West RM, Dumesic JA. Conversion of cellulose
[818] Michel C, Zaffran J, Ruppert AM, Matras-Michalska J, Jedrzejczyk M, Grams to hydrocarbon fuels by progressive removal of oxygen. Appl Catal B: Environ
J, et al. Role of water in metal catalyst performance for ketone hydrogenation: 2010;100:1849.
a joint experimental and theoretical study on levulinic acid conversion into [847] Lange JP, Vestering JZ, Haan RJ. Towards bio-based Nylon: conversion of
gamma-valerolactone. Chem Commun 2014;50:124503. -valerolactone to methyl pentenoate under catalytic distillation conditions.
[819] Bond JQ, Alonso DM, West RM, Dumesic JA. -Valerolactone ring-opening Chem Commun 2007;348890.
and decarboxylation over SiO2/Al2O3 in the presence of water. Langmuir [848] Meessen P, Vogt D, Keim W. Highly regioselective hydroformylation of
2010;26:162918. internal, functionalized olens applying PtSn complexes with large bite angle
[820] Lemonidou AA, Lpez L, Manzer LE, Barteau MA. Dynamic microbalance diphosphines. J Organomet Chem 1998;551:16570.
studies of RbOx/SiO2 catalyst deactivation/regeneration for -methylene [849] Manzer LE. Catalytic synthesis of -methylene--valerolactone: a biomass-
-valerolactone synthesis. Appl Catal A Gen 2004;272:2418. derived acrylic monomer. Appl Catal A Gen 2004;272:24956.
[821] Serrano-Ruiz JC, Dumesic JA. Catalytic routes for the conversion of biomass [850] Arasa M, Pethrick RA, Mantecn A, Serra A. New thermosetting
into liquid hydrocarbon transportation fuels. Energy Environ Sci 2011;4:83 nanocomposites prepared from diglycidyl ether of bisphenol and
99. -valerolactone initiated by rare earth triate initiators. Eur Polym J
[822] Yan K, Chen A. Selective hydrogenation of furfural and levulinic acid to 2010;46:513.
biofuels on the ecofriendly CuFe catalyst. Fuel 2014;115:1018. [851] Raoufmoghaddam S, Rood MTM, Buijze FKW, Drent E, Bouwman E. Catalytic
[823] Bozell JJ, Moens L, Elliott DC, Wang Y, Neuenscwander GG, Fitzpatrick SW, conversion of -valerolactone to -caprolactam: towards Nylon from
et al. Production of levulinic acid and use as a platform chemical for derived renewable feedstock. ChemSusChem 2014;7:198490.
products. Resour Conserv Recy 2000;28:22739. [852] Chalid M, Heeres HJ, Broekhuis AA. Ring-opening of -valerolactone with
[824] Du XL, Bi QY, Liu YM, Cao Y, He HY, Fan KN. Tunable copper-catalyzed amino compounds. J Appl Polym Sci 2012;123:355664.
chemoselective hydrogenolysis of biomass-derived -valerolactone into [853] Huo W, Zhang C, Yuan H, Jia M, Ning C, Tang Y, et al. Vapor-phase selective
1,4-pentanediol or 2-methyltetrahydrofuran. Green Chem 2012;14:9359. hydrogenation of maleic anhydride to succinic anhydride over Ni/TiO2
[825] Upare PP, Lee JM, Hwang YK, Hwang DW, Lee JH, Halligudi SB, et al. Direct catalysts. J Int Eng Chem 2014;20:41405.
hydrocyclization of biomass-derived levulinic acid to 2-methyltetrahydrofuran [854] Huang Y, Ma Y, Cheng Y, Wang L, Li X. Active ruthenium catalysts prepared
over nanocomposite copper/silica catalysts. ChemSusChem 2011;4:1749 by Cacumen Platycladi leaf extract for selective hydrogenation of maleic
52. anhydride. Appl Catal A Gen 2015;495:12430.
[826] Al-Shaal MG, Dzierbinski A, Palkovits R. Solvent-free -valerolactone [855] Regenhardt SA, Trasarti AF, Meyer CI, Garetto TF, Marchi AJ. Selective
hydrogenation to 2-methyltetrahydrofuran catalysed by Ru/C: a reaction gas-phase conversion of maleic anhydride to propionic acid on Pt-based
network analysis. Green Chem 2014;16:135864. catalysts. Catal Commun 2013;35:5963.
[827] Bond JQ, Wang D, Alonso DM, Dumesic JA. Interconversion between [856] Li M, Li G, Li N, Wang A, Dong W, Wang X, et al. Aqueous phase hydrogenation
-valerolactone and pentenoic acid combined with decarboxylation to form of levulinic acid to 1,4-pentanediol. Chem Commun 2014;50:141416.
butene over silica/alumina. J Catal 2011;281:2909. [857] Corbel-Demailly L, Ly BK, Minh DP, Tapin B, Especel C, Epron F, et al.
[828] Voge HH, May NC. Isomerization equilibria among the n-butenes. J Am Chem Heterogeneous catalytic hydrogenation of biobased levulinic and succinic
Soc 1946;68:5503. acids in aqueous solutions. ChemSusChem 2013;6:238895.
H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194 189

[858] Braden DJ, Henao CA, Heltzel J, Maravelias CC, Dumesic JA. Production of [888] Idem RO, Katikaneni SPR, Sethuraman R, Bakhshi NN. Production of C4
liquid hydrocarbon fuels by catalytic conversion of biomass-derived levulinic hydrocarbons from modied Fischer-Tropsch synthesis over Co-Ni-ZrO2/
acid. Green Chem 2011;13:175565. sulfated-ZrO2 hybrid catalysts. Energy Fuels 2000;14:107282.
[859] Touchy AS, Siddiki SMAH, Kon K, Shimizu K. Heterogeneous Pt catalysts for [889] Sartipi S, Makkee M, Kapteijn F, Gascon J. Catalysis engineering of bifunctional
reductive amination of levulinic acid to pyrrolidones. ACS Catal 2014;4:3045 solids for the one-step synthesis of liquid fuels from syngas: a review. Catal
50. Sci Technol 2014;4:893907.
[860] Ding G, Zhu Y, Zheng H, Chen H, Li Y. Vapour phase hydrogenolysis of [890] Yu W, Tang Y, Mo L, Chen P, Lou H, Zheng X. One-step hydrogenation
biomass-derived diethyl succinate to tetrahydrofuran over CuOZnO/solid esterication of furfural and acetic acid over bifunctional Pd catalysts for
acid bifunctional catalysts. J Chem Technol Biotechnol 2011;86:2317. bio-oil upgrading. Bioresour Technol 2011;102:82416.
[861] Zhao M, Yang X, Church TL, Harris AT. Novel CaOSiO 2 sorbent and [891] Yu W, Tang Y, Mo L, Chen P, Lou H, Zheng X. Bifunctional Pd/Al-SBA-15
bifunctional Ni/CoCaO/SiO2 complex for selective H2 synthesis from cellulose. catalyzed one-step hydrogenationesterication of furfural and acetic acid:
Environ Sci Technol 2012;46:297683. a model reaction for catalytic upgrading of bio-oil. Catal Commun
[862] Shimura K, Yoshida H. Heterogeneous photocatalytic hydrogen production 2011;13:359.
from water and biomass derivatives. Energy Environ Sci 2011;4:2467 [892] Lewis JD, Van de Vyver S, Crisci AJ, Gunther WR, Michaelis VK, Grin RG,
81. et al. A continuous ow strategy for the coupled transfer hydrogenation and
[863] Takahashi T, Ueno K, Kai T. Vapor phase Beckmann rearrangement of etherication of 5-(hydroxymethyl)furfural using Lewis acid zeolites.
cyclopentanone oxime over high silica HZSM-5 zeolites. Micropor Mater ChemSusChem 2014;7:225565.
1993;1:3237. [893] Zhang X, Wang T, Ma L, Wu C. Aqueous-phase catalytic process for production
[864] Scognamiglio J, Jones L, Letizia CS, Api AM. Fragrance material review on of pentane from furfural over nickel-based catalysts. Fuel 2010;89:2697702.
cyclopentanone. Food Chem Technol 2012;50:S60812. [894] Chen B, Li F, Huang Z, Yuan G. Tuning catalytic selectivity of liquid-phase
[865] Hronec M, Fulajtrova K, Liptaj T, tolcov M, Prnayov N, Sotk T. hydrogenation of furfural via synergistic effects of supported bimetallic
Cyclopentanone: a raw material for production of C15 and C17 fuel precursors. catalysts. Appl Catal A Gen 2015;500:239.
Biomass Bioenergy 2014;63:2919. [895] Huber GW, Dumesic JA. An overview of aqueous-phase catalytic processes
[866] Akashi T, Sato S, Takahashi R, Sodesawa T, Inui K. Catalytic vapor-phase for production of hydrogen and alkanes in a biorenery. Catal Today
cyclization of 1,6-hexanediol into cyclopentanone. Catal Commun 2006;111:11932.
2003;4:41116. [896] Davda RR, Shabaker JW, Huber GW, Cortright D, Dumesic JA. A review of
[867] Dubkov KA, Panov GI, Starokon EV, Parmon VN. Non-catalytic liquid phase catalytic issues and process conditions for renewable hydrogen and alkanes
oxidation of alkenes with nitrous oxide. 2. Oxidation of cyclopentene to by aqueous-phase reforming of oxygenated hydrocarbons over supported
cyclopentanone. React Kinet Catal Lett 2002;77:197205. metal catalysts. Appl Catal B: Environ 2005;56:17186.
[868] Hronec M, Fulajtrova K, Sotk T. Highly selective rearrangement of furfuryl [897] Kim YT, Dumesic JA, Huber GW. Aqueous-phase hydrodeoxygenation of
alcohol to cyclopentanone. Appl Catal B: Environ 2014;154:294300. sorbitol: a comparative study of Pt/Zr phosphate and PtAReOx/C. J Catal
[869] Hronec M, Fulajtarov K. Selective transformation of furfural to 2013;304:7285.
cyclopentanone. Catal Commun 2012;24:1004. [898] de Beeck BO, Michie D, Geboers J, Holsbeek J, Morr E, Oswald S, et al. Direct
[870] Zhou M, Zeng Z, Zhu H, Xiao G, Xiao R. Aqueous-phase catalytic hydrogenation catalytic conversion of cellulose to liquid straight-chain alkanes. Energy
of furfural to cyclopentanol over Cu-Mg-Al hydrotalcites derived catalysts: Environ Sci 2015;8:23040.
model reaction for upgrading of bio-oil. J Energy Chem 2014;23:916. [899] Liu S, Tamura M, Nakagawa Y, Tomishige K. One-pot conversion of cellulose
[871] Yang Y, Du Z, Huang Y, Lu F, Wang F, Gao J, et al. Conversion of furfural into into n-hexane over the Ir-ReOx/SiO2 catalyst combined with HZSM-5. ACS
cyclopentanone over NiCu bimetallic catalysts. Green Chem 2013;15:1932 Sust Chem Eng 2014;2:181927.
40. [900] Sen SM, Alonso DM, Wettstein SG, Grbz EI, Henao CA, Dumesic JA, et al.
[872] Hronec M, Fulajtarov K, Liptaj T. Effect of catalyst and solvent on the furan A sulfuric acid management strategy for the production of liquid hydrocarbon
ring rearrangement to cyclopentanone. Appl Catal A Gen 2012;437-8:10411. fuels via catalytic conversion of biomass-derived levulinic acid. Energy
[873] Hronec M, Fulajtrova K, Micuik M. Inuence of furanic polymers on Environ Sci 2012;5:96907.
selectivity of furfural rearrangement to cyclopentanone. Appl Catal A Gen [901] Zhao Y, Fu Y, Guo QX. Production of aromatic hydrocarbons through catalytic
2013;468:42631. pyrolysis of -valerolactone from biomass. Bioresour Technol 2012;114:7404.
[874] Ohyama J, Kanao R, Esaki A, Satsuma A. Conversion of 5- [902] Pupovac K, Palkovits R. Cu/MgAl 2 O 4 as bifunctional catalyst for aldol
hydroxymethylfurfural to a cyclopentanone derivative by ring rearrangement condensation of 5-hydroxymethylfurfural and selective transfer
over supported Au nanoparticles. Chem Commun 2014;50:56336. hydrogenation. ChemSusChem 2013;6:210310.
[875] Chen X, Sun W, Xiao N, Yan Y, Liu S. Experimental study for liquid phase [903] Yati I, Yeom M, Choi JW, Choo H, Suh DJ, Ha JM. Water-promoted selective
selective hydrogenation of furfuryl alcohol to tetrahydrofurfuryl alcohol on heterogeneous catalytic trimerization of xylose-derived 2-methylfuran to
supported Ni catalysts. Chem Eng J 2007;126:511. diesel precursors. Appl Catal A Gen 2015;495:2005.
[876] Zhang B, Zhu Y, Ding G, Zheng H, Li Y. Selective conversion of furfuryl alcohol [904] Liu D, Chen EYX. Integrated catalytic process for biomass conversion and
to 1,2-pentanediol over a Ru/MnOx catalyst in aqueous phase. Green Chem upgrading to C12 furoin and alkane fuel. ACS Catal 2014;4:130210.
2012;14:34029. [905] Liu D, Chen EYX. Diesel and alkane fuels from biomass by organocatalysis
[877] Mizugaki T, Yamakawa T, Nagatsu Y, Maeno Z, Mitsudome T, Jitsukawa K, and metalacid tandem catalysis. ChemSusChem 2013;6:22369.
et al. Direct transformation of furfural to 1,2-pentanediol using a hydrotalcite- [906] Chheda JN, Dumesic JA. An overview of dehydration, aldol-condensation and
supported platinum nanoparticle catalyst. ACS Sust Chem Eng 2014;2:2243 hydrogenation processes for production of liquid alkanes from biomass-
7. derived carbohydrates. Catal Today 2007;123:5970.
[878] Liu S, Amada Y, Tamura M, Nakagawa Y, Tomishige K. One-pot selective [907] Dedsuksophon W, Faungnawakij K, Champreda V, Laosiripojana N.
conversion of furfural into 1,5-pentanediol over a Pd-added IrReOx/SiO2 Hydrolysis/dehydration/aldol-condensation/hydrogenation of lignocellulosic
bifunctional catalyst. Green Chem 2014;16:61726. biomass and biomass-derived carbohydrates in the presence of Pd/WO3ZrO2
[879] Liu S, Amada Y, Tamura M, Nakagawa Y, Tomishige K. Performance and in a single reactor. Bioresour Technol 2011;102:20406.
characterization of rheniummodied RhIr alloy catalyst for one-pot [908] Zakzeski J, Bruijnincx PCA, Jongerius AL, Weckhuysen BM. The catalytic
conversion of furfural into 1,5-pentanediol. Catal Sci Technol 2014;4:2535 valorization of lignin for the production of renewable chemicals. Chem Rev
49. 2010;110:355299.
[880] Xu W, Wang H, Liu X, Ren J, Wang Y, Lu G. Direct catalytic conversion of [909] Liu H, Jiang T, Han B, Liang S, Zhou Y. Selective phenol hydrogenation to
furfural to 1,5-pentanediol by hydrogenolysis of the furan ring under mild cyclohexanone over a dual supported PdLewis acid catalyst. Science
conditions over Pt/Co2AlO4 catalyst. Chem Commun 2011;47:39246. 2009;326:12502.
[881] Li F, Lu T, Chen B, Huang Z, Yuan G. Pt nanoparticles over TiO2ZrO2 mixed [910] Deutsch KL, Shanks BH. Hydrodeoxygenation of lignin model compounds
oxide as multifunctional catalysts for an integrated conversion of furfural over a copper chromite catalyst. Appl Catal A Gen 2012;447-8:14450.
to 1,4-butanediol. Appl Catal A Gen 2014;478:2528. [911] Laskar DD, Tucker MP, Chen X, Helms GL, Yang B. Noble-metal catalyzed
[882] Nakagawa Y, Tamura M, Tomishige K. Catalytic materials for the hydrodeoxygenation of biomass-derived lignin to aromatic hydrocarbons.
hydrogenolysis of glycerol to 1,3-propanediol. J Mater Chem A 2014;2:6688 Green Chem 2014;16:897910.
702. [912] Ji N, Wang X, Weidenthaler C, Spliethoff B, Rinaldi R. Iron(II) disuldes as
[883] Tuteja J, Choudhary H, Nishimura S, Ebitani K. Direct synthesis of 1,6- precursors of highly selective catalysts for hydrodeoxygenation of dibenzyl
hexanediol from HMF over a heterogeneous Pd/ZrP catalyst using formic acid ether into toluene. ChemCatChem 2015;7:9606.
as hydrogen source. ChemSusChem 2014;7:96100. [913] Wang X, Rinaldi R. A route for lignin and bio-oil conversion: dehydroxylation
[884] Mortensen PM, Grunwaldt JD, Jensena PA, Knudsen KG, Jensen AD. A review of phenols into arenes by catalytic tandem reactions. Angew Chem Int Ed
of catalytic upgrading of bio-oil to engine fuels. Appl Catal A Gen 2013;52:11499503.
2011;407:119. [914] Zhang W, Chen J, Liu R, Wang S, Chen L, Li K. Hydrodeoxygenation of
[885] Choudhary TV, Phillips CB. Renewable fuels via catalytic hydrodeoxygenation. lignin-derived phenolic monomers and dimers to alkane fuels over
Appl Catal A Gen 2011;397:112. bifunctional zeolite-supported metal catalysts. ACS Sust Chem Eng
[886] Xiu S, Shahbazi A. Bio-oil production and upgrading research: a review. Renew 2014;2:68391.
Sust Energy Rev 2012;16:440614. [915] Corma A, Iborra S, Velty A. Chemical routes for the transformation of biomass
[887] Cheng K, Kang J, Huang S, You Z, Zhang Q, Ding J, et al. Mesoporous Beta into chemicals. Chem Rev 2007;107:2411502.
zeolite-supported ruthenium nanoparticles for selective conversion of [916] Besson M, Gallezot P, Pinel C. Conversion of biomass into chemicals over
synthesis gas to C5C11 isoparans. ACS Catal 2012;2:4419. metal catalysts. Chem Rev 2014;114:182770.
190 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

[917] Straathof AJJ. Transformation of biomass into commodity chemicals using [945] Kwon Y, Koper MTM. Electrocatalytic hydrogenation and deoxygenation of
enzymes or cells. Chem Rev 2014;114:1871908. glucose on solid metal electrodes. ChemSusChem 2013;6:45562.
[918] Asadieraghi M, Daud WMAW, Abbas HF. Heterogeneous catalysts for [946] Kwon Y, de Jong E, van der Waal JK, Koper MTM. Selective electrocatalytic
advanced bio-fuel production through catalytic biomass pyrolysis vapor oxidation of sorbitol to fructose and sorbose. ChemSusChem 2015;8:9703.
upgrading: a review. RSC Adv 2015;5:2223455. [947] Reichert E, Wintringer R, Volmer DA, Hempelmann R. Electro-catalytic
[919] Xuan J, Leung MKH, Leung DYC, Ni M. A review of biomass-derived fuel oxidative cleavage of lignin in a protic ionic liquid. Phys Chem Chem Phys
processors for fuel cell systems. Renew Sust Energy Rev 2009;13:130113. 2012;14:521421.
[920] Tominaga M, Shimazoe T, Nagashima M, Taniguchi I. Electrocatalytic oxidation [948] Lam CH, Lowe CB, Li Z, Longe KN, Rayburn JT, Caldwell MA, et al.
of glucose at gold nanoparticle-modied carbon electrodes in alkaline and Electrocatalytic upgrading of model lignin monomers with earth abundant
neutral solutions. Electrochem Commun 2005;7:18993. metal electrodes. Green Chem 2015;17:6019.
[921] Yi Q, Yu W, Niu F. Novel nanoporous binary Au-Ru electrocatalysts for glucose [949] Vuyyuru KR, Strasser P. Oxidation of biomass derived 5-
oxidation. Electroanal 2010;22:55663. hydroxymethylfurfural using heterogeneous and electrochemical catalysis.
[922] Ci S, Wen Z, Mao S, Hou Y, Cui S, He Z, et al. One-pot synthesis of high- Catal Today 2012;195:14454.
performance Co/graphene electrocatalysts for glucose fuel cells free of [950] Chadderdon DJ, Xin L, Qi J, Qiu Y, Krishna P, More KL, et al. Electrocatalytic
enzymes and precious metals. Chem Commun 2015;51:93547. oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid on
[923] Liu A, Ren Q, Xu T, Yuan M, Tang W. Morphology-controllable gold supported Au and Pd bimetallic nanoparticles. Green Chem 2014;16:3778
nanostructures on phosphorus doped diamond-like carbon surfaces and their 86.
electrocatalysis for glucose oxidation. Sensor Actuat B: Chem 2012;162:135 [951] Kwon Y, de Jong E, Raoufmoghaddam S, Koper MTM. Electrocatalytic
42. hydrogenation of 5-hydroxymethylfurfural in the absence and presence of
[924] Xia C, Ning W. A novel non-enzymatic electrochemical glucose sensor glucose. ChemSusChem 2013;6:165967.
modied with FeOOH nanowire. Electrochem Commun 2010;12:15814. [952] Kwon Y, Birdja YY, Raoufmoghaddam S, Koper MTM. Electrocatalytic
[925] Karczmarczyk A, Celebanska A, Nogala W, Sashuk V, Chernyaeva O, Opallo hydrogenation of 5-hydroxymethylfurfural in acidic solution. ChemSusChem
M. Electrocatalytic glucose oxidation at gold and gold-carbon nanoparticulate 2015;8:174551.
lm prepared from oppositely charged nanoparticles. Electrochim Acta [953] Nilges P, Schrder U. Electrochemistry for biofuel generation: production of
2014;117:21116. furans by electrocatalytic hydrogenation of furfurals. Energy Environ Sci
[926] Shi Q, Diao G, Mu S. The electrocatalytic oxidation of glucose on the bimetallic 2013;6:292531.
Au-Ag particles-modied reduced graphene oxide electrodes in alkaline [954] Chu D, Hou Y, He J, Xu M, Wang Y, Wang S, et al. Nano TiO2 lm electrode
solutions. Electrochim Acta 2014;133:33546. for electrocatalytic reduction of furfural in ionic liquids. J Nanopart Res
[927] Li R, Zhang J, Wang Z, Li Z, Liu J, Gu Z, et al. Novel graphene-gold nanohybrid 2009;11:18059.
with excellent electrocatalytic performance for the electrochemical detection [955] Li Z, Kelkar S, Lam CH, Luczek K, Jackson JE, Miller DJ, et al. Aqueous
of glucose. Sensor Actuat B: Chem 2015;208:4218. electrocatalytic hydrogenation of furfural using a sacricial anode.
[928] Jiang T, Yan L, Meng Y, Xiao M, Wu Z, Tsiakaras P, et al. Glucose Electrochim Acta 2012;64:8793.
electrooxidation in alkaline medium: performance enhancement of PdAu/C [956] Zhao B, Chen M, Guo Q, Fu Y. Electrocatalytic hydrogenation of furfural to
synthesized by NH3 modied pulse microwave assisted polyol method. Appl furfuryl alcohol using platinum supported on activated carbon bers.
Catal B: Environ 2015;162:27581. Electrochim Acta 2014;135:13946.
[929] Zhang S, Han L, Hou C, Li C, Lang Q, Han L, et al. Novel glucose sensor with [957] Wang F, Xu M, Wei L, Wei Y, Hu Y, Fang W, et al. Fabrication of La-doped
Au@Ag heterogeneous nanorods based on electrocatalytic reduction of TiO2 lm electrode and investigation of its electrocatalytic activity for furfural
hydrogen peroxide at negative potential. J Electroanal Chem 2015;742:849. reduction. Electrochim Acta 2015;153:1704.
[930] Devadoss A, Sudhagar P, Das S, Lee SY, Terashima C, Nakata K, et al. Synergistic [958] Green SK, Lee J, Kim HJ, Tompsett GA, Kim WB, Huber GW. The
metalmetal oxide nanoparticles supported electrocatalytic graphene for electrocatalytic hydrogenation of furanic compounds in a continuous
improved photoelectrochemical glucose oxidation. ACS Appl Mater Interfaces electrocatalytic membrane reactor. Green Chem 2013;15:186979.
2014;6:486471. [959] Xin L, Zhang Z, Qi J, Chadderdon DJ, Qiu Y, Warsko KM, et al. Electricity storage
[931] Ma C, Xue W, Li J, Xing W, Hao Z. Mesoporous carbon-conned Au catalysts in biofuels: selective electrocatalytic reduction of levulinic acid to valeric
with superior activity for selective oxidation of glucose to gluconic acid. Green acid or -valerolactone. ChemSusChem 2013;6:67486.
Chem 2013;15:103541. [960] Qiu Y, Xin L, Chadderdon DJ, Qi J, Liang C, Li W. Integrated electrocatalytic
[932] Li Y, Niu X, Tang J, Lan M, Zhao H. A comparative study of nonenzymatic processing of levulinic acid and formic acid to produce biofuel intermediate
electrochemical glucose sensors based on Pt-Pd nanotube and nanowire valeric acid. Green Chem 2014;16:130515.
arrays. Electrochim Acta 2014;130:18. [961] Luo W, Bruijnincx PCA, Weckhuysen BM. Selective, one-pot catalytic
[933] Brouzgou A, Yan LL, Song SQ, Tsiakaras P. Glucose electrooxidation over conversion of levulinic acid to pentanoic acid over Ru/H-ZSM5. J Catal
Pd x Rh/C electrocatalysts in alkaline medium. Appl Catal B: Environ 2014;320:3341.
2014;147:4819. [962] Yang Y, Gao G, Zhang X, Li F. Facile fabrication of composition-tuned RuNi
[934] Chen CC, Lin CL, Chen LC. Functionalized carbon nanomaterial supported bimetallics in ordered mesoporous carbon for levulinic acid hydrogenation.
palladium nano-catalysts for electrocatalytic glucose oxidation reaction. ACS Catal 2014;4:141925.
Electrochim Acta 2015;152:40816. [963] Fashedemi OO, Ozoemena KI. Comparative electrocatalytic oxidation of
[935] Huo H, Xu Z, Zhang T, Xu C. Ni/CdS/TiO2 nanotube array heterostructures ethanol, ethylene glycol and glycerol in alkaline medium at Pd-decorated
for high performance photoelectrochemical biosensing. J Mater Chem A FeCo@Fe/C core-shell nanocatalysts. Electrochim Acta 2014;128:27986.
2015;3:58828. [964] Yang L, Kinoshita S, Yamada T, Kanda S, Kitagawa H, Tokunaga M, et al. A
[936] Long M, Tan L, Liu H, He Z, Tang A. Novel helical TiO2 nanotube arrays metalorganic framework as an electrocatalyst for ethanol oxidation. Angew
modied by Cu2O for enzyme-free glucose oxidation. Biosens Bioelectron Chem 2010;122:54769.
2014;59:24350. [965] Zheng JN, Lv JJ, Li SS, Xue MW, Wang AJ, Feng JJ. One-pot synthesis of reduced
[937] Li SJ, Xia N, Lv XL, Zhao MM, Yuan BQ, Pang H. A facile one-step graphene oxide supported hollow Ag@Pt coreshell nanospheres with
electrochemical synthesis of graphene/NiO nanocomposites as ecient enhanced electrocatalytic activity for ethylene glycol oxidation. J Mater Chem
electrocatalyst for glucose and methanol. Sensor Actuat B: Chem A 2014;2:344551.
2014;190:80917. [966] Ramulifho T, Ozoemena KI, Modibedi RM, Jafta CJ, Mathe MK. Electrocatalytic
[938] Wu J, Miao Y, Liang X, Yang Z, Yang Y, Ouyang R. Promotion effect of bismuth oxidation of ethylene glycol at palladium-bimetallic nanocatalysts (PdSn and
on nickel electrodeposition and its electrocatalysis to glucose oxidation. PdNi) supported on sulfonate-functionalised multi-walled carbon nanotubes.
Electroanal 2014;26:85663. J Electroanal Chem 2013;692:2630.
[939] Gu Y, Liu Y, Yang H, Li B, An Y. Electrocatalytic glucose oxidation via hybrid [967] Kim HJ, Lee J, Green SK, Huber GW, Kim WB. Selective glycerol oxidation by
nanomaterial catalyst of multi-wall TiO2 nanotubes supported Ni(OH)2 electrocatalytic dehydrogenation. ChemSusChem 2014;7:10516.
nanoparticles: optimization of the loading level. Electrochim Acta [968] Wang H, Thia L, Li N, Ge X, Liu Z, Wang X. Pd nanoparticles on carbon
2015;160:26370. nitride-graphene for the selective electro-oxidation of glycerol in alkaline
[940] Arvinte A, Sesay AM, Virtanen V. Carbohydrates electrocatalytic oxidation solution. ACS Catal 2015;5:317480.
using CNTNiCo-oxide modied electrodes. Talanta 2011;84:1806. [969] Hickey DP, McCammant MS, Giroud F, Sigman MS, Minteer SD. Hybrid
[941] Li L, Liang B, Shi J, Li F, Mascini M, Liu A. A selective and sensitive D-xylose enzymatic and organic electrocatalytic cascade for the complete oxidation
electrochemical biosensor based on xylose dehydrogenase displayed on the of glycerol. J Am Chem Soc 2014;136:1591720.
surface of bacteria and multi-walled carbon nanotubes modied electrode. [970] Wang J, Huang L, Yang R, Zhang Z, Wu J, Gao Y, et al. Recent advances in solid
Biosens Bioelectron 2012;33:1005. sorbents for CO2 capture and new development trends. Energy Environ Sci
[942] Xu D, Luo L, Ding Y, Jiang L, Zhang Y, Ouyang X, et al. A novel nonenzymatic 2014;7:3478518.
fructose sensor based on electrospun LaMnO3 bers. J Electroanal Chem [971] Cole AJ, Mata L, Paul NA, de Nys R. Using CO2 to enhance carbon capture and
2014;727:216. biomass applications of fresh water macroalgae. GCB Bioen 2014;6:637
[943] Jokic A, Ristic N, Jaksic MM, Spasojevic M, Krstajic N. Simultaneous electrolytic 45.
production of xylitol and xylonic acid from xylose. J Appl Electrochem [972] Inglis JL, MacLean BJ, Pryce MT, Vos JG. Electrocatalytic pathways towards
1991;21:3216. sustainable fuel production from water and CO 2 . Coordin Chem Rev
[944] Aissa AA, Ader M. Electro-catalytic isomerization of lactose into lactulose: 2012;256:2571600.
the impact of the electric current, temperature and reactor conguration. [973] Oh Y, Hu X. Organic molecules as mediators and catalysts for photocatalytic
Int Dairy J 2014;34:21319. and electrocatalytic CO2 reduction. Chem Soc Rev 2013;42:225361.
H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194 191

[974] Kuhl KP, Hatsukade T, Cave ER, Abram DN, Kibsgaard J, Jaramillo TF. 5-hydroxymethylfurfural, levulinic, and formic acids. Ind Eng Chem Res
Electrocatalytic conversion of carbon dioxide to methane and methanol on 2007;46:770310.
transition metal surfaces. J Am Chem Soc 2014;136:1410713. [1003] Girsuta B, Janssen LPBM, Heeres HJ. Kinetic study on the acid-catalyzed
[975] Chen WF, Iyer S, Iyer S, Sasaki K, Wang CH, Zhu Y, et al. Biomass-derived hydrolysis of cellulose to levulinic acid. Ind Eng Chem Res 2007;46:1696708.
electrocatalytic composites for hydrogen evolution. Energy Environ Sci [1004] Dutta S. Catalytic materials that improve selectivity of biomass conversions.
2013;6:181826. RSC Adv 2012;2:1257593.
[976] Xie S, Zhai T, Li W, Yu M, Liang C, Gan J, et al. Hydrogen production from [1005] Zheng Y, Pan Z, Zhan R. Overview of biomass pretreatment for cellulosic
solar driven glucose oxidation over Ni(OH)2 functionalized electroreduced- ethanol production. Int J Agric Biol 2009;2:5168.
TiO2 nanowire arrays. Green Chem 2013;15:243440. [1006] Hendriks ATWM, Zeeman G. Pretreatments to enhance the digestibility of
[977] Ni M, Leung DYC, Leung MKH. A review on reforming bio-ethanol for lignocellulosic biomass. Bioresour Technol 2009;100:1018.
hydrogen production. Int J Hydrogen Energy 2007;32:323847. [1007] Guo F, Fang Z, Xu CC, Smith RL. Solid acid mediated hydrolysis of biomass
[978] Marr AC, Liu S. Combining bio- and chemo-catalysis: from enzymes to cells, for producing biofuels. Prog Energy Combust Sci 2012;38:67290.
from petroleum to biomass. Trends Biotechnol 2011;29:199204. [1008] Saritha M, Arora A, Lata. Biological pretreatment of lignocellulosic substrates
[979] Vennestrm PNR, Christensen CH, Pedersen S, Grunwaldt JD, Woodley JM. for enhanced delignication and enzymatic digestibility. Ind J Microbiol
Next-generation catalysis for renewables: combining enzymatic with 2012;52:12230.
inorganic heterogeneous catalysis for bulk chemical production. [1009] Bak JS, Kim MD, Choi IG, Kim KH. Biological pretreatment of rice straw by
ChemCatChem 2010;2:24958. fermenting with Dichomitus squalens. New Biotechnol 2010;27:42434.
[980] Wongnate T, Sucharitakul J, Chaiyen P. Identication of a catalytic base for [1010] Prajapati SK, Bhattachary A, Malik A, Vijay VK. Pretreatment of algal biomass
sugar oxidation in the pyranose 2-oxidase reaction. Chembiochem using fungal crude enzymes. Algal Res 2015;8:814.
2011;12:257786. [1011] Mosier N, Wyman C, Dale B, Elander R, Lee YY, Holtzapple M, et al. Features
[981] Leitner C, Neuhauser W, Volc J, Kulbe KD, Nidetzky B, Haltrich D. The Cetus of promising technologies for pretreatment of lignocellulosic biomass.
process revisited: a novel enzymatic alternative for the production of Bioresour Technol 2005;96:67386.
aldose-free D-fructose. Biocatal Biotransform 1998;16:36582. [1012] Krcher MA, Iqbal Y, Lewandowski I, Senn T. Comparing the performance
[982] Lee YC, Chen CT, Chiu YT, Wu KCW. An effective cellulose-to-glucose-to- of Miscanthus x giganteus and wheat straw biomass in sulfuric acid based
fructose conversion sequence by using enzyme immobilized Fe3O4-loaded pretreatment. Bioresour Technol 2015;180:3604.
mesoporous silica nanoparticles as recyclable biocatalysts. ChemCatChem [1013] Sun Y, Cheng JY. Hydrolysis of lignocellulosic materials for ethanol
2013;5:21537. production: a review. Bioresour Technol 2002;83:111.
[983] Sthlberg T, Woodley JM, Riisager A. Enzymatic isomerization of glucose and [1014] de Almeida RM, Li JR, Nederlof C, OConnor P, Makkee M, Moulijn JA. Cellulose
xylose in ionic liquids. Catal Sci Technol 2012;2:2915. conversion to isosorbide in molten salt hydrate media. ChemSusChem
[984] Lee YC, Dutta S, Wu KCW. Integrated, cascading enzyme-/chemocatalytic 2010;3:3258.
cellulose conversion using catalysts based on mesoporous silica nanoparticles. [1015] Okatova OV, Lavrenko PN, Cvetkov VN, Dautzenberg H, Philipp B. Viscometric
ChemSusChem 2014;7:32416. and diffusion investigations in the cellulose/cadoxen/water system. Acta
[985] Huang H, Denard CA, Alamillo R, Crisci AJ, Miao Y, Dumesic JA, et al. Tandem Polym 2003;40:297301.
catalytic conversion of glucose to 5-hydroxymethylfurfural with an [1016] Ramos LA, Frollini E, Heinze T. Carboxymethylation of cellulose in the new
immobilized enzyme and a solid acid. ACS Catal 2014;4:21658. solvent dimethyl sulfoxide/tetrabutylammonium uoride. Carbohyd Polym
[986] Grande PM, Bergs C, Domnguez de Mara P. Chemo-enzymatic conversion 2005;60:25967.
of glucose into 5-hydroxymethylfurfural in seawater. ChemSusChem [1017] Song YB, Zhou JP, Zhang LN, Wu XJ. Homogenous modication of cellulose
2012;5:12036. with acrylamide in NaOH/urea aqueous solutions. Carbohyd Polym
[987] Boisen A, Christensen TB, Fu W, Gorbanev YY, Hansen TS, Jensen JS, et al. 2008;73:1825.
Process integration for the conversion of glucose to 2,5-furandicarboxylic [1018] Ishii D, Tatsumi D, Matsumoto T. Effect of solvent exchange on the
acid. Chem Eng Res Des 2009;87:131827. supramolecular structure, the molecular mobility and the dissolution
[988] Krystof M, Prez-Snchez M, Domnguez de Mara P. Lipase-mediated behavior of cellulose in LiCl/DMAc. Carbohyd Res 2008;343:91928.
selective oxidation of furfural and 5-hydroxymethylfurfural. ChemSusChem [1019] Tadesse H, Luque R. Advances on biomass pretreatment using ionic liquids:
2013;6:82630. an overview. Energy Environ Sci 2011;4:391329.
[989] Koopman F, Wierckx N, de Winde JH, Ruijssenaars HJ. Ecient whole-cell [1020] Swatloski RP, Spear SK, Holbrey JD, Rogers RD. Dissolution of cellose with
biotransformation of 5-(hydroxymethyl)furfural into FDCA, 2,5- ionic liquids. J Am Chem Soc 2002;124:49745.
furandicarboxylic acid. Bioresour Technol 2010;101:62916. [1021] Kamiya N, Matsushita Y, Hanaki M, Nakashima K, Narita M, Goto M, et al.
[990] Boopathy R. Anaerobic biotransformation of furfural to furfuryl alcohol by Enzymatic in-situ saccharication of cellulose in aqueous-ionic liquid media.
a methanogenic archaebacterium. Int Biodeter Biodegr 2009;63:10702. Biotechnol Lett 2008;30:103740.
[991] Zhang Y, Han B, Ezeji TC. Biotransformation of furfural and 5-hydroxymethyl [1022] Jiang LQ, Fang Z, Zhao ZL, He F, Li HB. 2,3-Butanediol and acetoin production
furfural (HMF) by Clostridium acetobutylicum ATCC 824 during butanol from enzymatic hydrolysate of ionic liquid-pretreated cellulose by
fermentation. New Biotechnol 2012;29:34551. Paenibacillus polymyxa. Bioresources 2015;10:131829.
[992] Martin CH, Wu D, Prather KLJ. Integrated bioprocessing for the pH-dependent [1023] Jiang LQ, Fang Z, Li XK, Luo J, Fan SP. Combination of dilute acid and ionic
production of 4-valerolactone from levulinate in Pseudomonas putida KT2440. liquid pretreatments of sugarcane bagasse for enzymatic saccharication.
Appl Environ Microbiol 2010;76:41724. Process Biochem 2013;48:19426.
[993] Gtz K, Liese A, Ansorge-Schumacher M, Hilterhaus L. A chemo-enzymatic [1024] Olivier-Bourbigou H, Magna L, Morvan D. Ionic liquids and catalysis: recent
route to synthesize (S)--valerolactone from levulinic acid. Appl Microbiol progress from knowledge to applications. Appl Catal A Gen 2010;373:156.
Biotechnol 2013;97:386573. [1025] Wang C, Wei Z, Wang L, Sun P, Wang Z. Assessment of bromide-based ionic
[994] Min K, Kim S, Yum T, Kim Y, Sang B-I, Um Y. Conversion of levulinic acid to liquid toxicity toward aquatic organisms and QSAR analysis. Ecotox Environ
2-butanone by acetoacetate decarboxylase from Clostridium acetobutylicum. Safe 2015;115:11218.
Appl Microbiol Biotechnol 2013;97:562734. [1026] Costa SPF, Pinto PCAG, Lapa RAS, Saraiva MLMFS. Toxicity assessment of ionic
[995] Multer A, McGraw N, Hohn K, Vadlani P. Production of methyl ethyl ketone liquids with Vibrio scheri: an alternative fully automated methodology. J
from biomass using a hybrid biochemical/catalytic approach. Ind Eng Chem Hazard Mater 2015;284:13642.
Res 2013;52:5660. [1027] Deng Y, Beadham I, Ghavre M, Costa Gomes MF, Gathergood N, Husson P,
[996] Grala A, Zielinski M, De bowski M, Dudek M. Effects of hydrothermal et al. When can ionic liquids be considered readily biodegradable?
depolymerization and enzymatic hydrolysis of algae biomass on yield of Biodegradation pathways of pyridinium, pyrrolidinium and ammonium-based
methane fermentation process. Pol J Environ Stud 2012;21:3616. ionic liquids. Green Chem 2015;17:147991.
[997] Nduko JM, Suzuki W, Matsumoto K, Kobayashi H, Ooi T, Fukuoka A, et al. [1028] Cheng YS, Chen KY, Chou TH. Concurrent calcium peroxide pretreatment and
Polyhydroxyalkanoates production from cellulose hydrolysate in Escherichia wet storage of water hyacinth for fermentable sugar production. Bioresour
coli LS5218 with superior resistance to 5-hydroxymethylfurfural. J Biosci Technol 2015;176:26772.
Bioeng 2012;113:702. [1029] da Costa JA, Marques JE, Gonalves LRB, Rocha MVP. Enhanced enzymatic
[998] Matsumoto K, Kobayashi H, Ikeda K, Komanoya T, Fukuoka A, Taguchi S. hydrolysis and ethanol production from cashew apple bagasse pretreated
Chemo-microbial conversion of cellulose into polyhydroxybutyrate through with alkaline hydrogen peroxide. Bioresour Technol 2015;179:24959.
ruthenium-catalyzed hydrolysis of cellulose into glucose. Bioresour Technol [1030] Ahring BK, Biswas R, Ahamed A, Teller PJ, Uellendahl H. Making lignin
2011;102:35647. accessible for anaerobic digestion by wet-explosion pretreatment. Bioresour
[999] Lopez M, Fort S, Bizot H, Bulon A, Driguez H. Chemo-enzymatic synthesis Technol 2015;175:1828.
of xylogluco-oligosaccharides and their interactions with cellulose. Carbohyd [1031] Ramadoss G, Muthukumar K. Inuence of dual salt on the pretreatment of
Polym 2012;88:18593. sugarcane bagasse with hydrogen peroxide for bioethanol production. Chem
[1000] You C, Chen H, Myung S, Sathitsuksanoh N, Ma H, Zhang XZ, et al. Enzymatic Eng J 2015;260:17887.
transformation of nonfood biomass to starch. Proc Natl Acad Sci USA [1032] Zhou L, Yang X, Xu J, Shi M, Wang F, Chen C, et al. Depolymerization of
2013;110:71827. cellulose to glucose by oxidationhydrolysis. Green Chem 2015;17:151924.
[1001] Colmenares JC, Luque R. Heterogeneous photocatalytic nanomaterials: [1033] Wang YZ, Chen X, Wang Z, Zhao JF, Fan TT, Li DS, et al. Effect of low
prospects and challenges in selective transformations of biomass-derived concentration alkali and ultrasound combination pretreatment on biogas
compounds. Chem Soc Rev 2014;43:76578. production by stalk. Adv Mat Res 2011;383:34347.
[1002] Asghari FS, Yoshida H. Kinetics of the decomposition of fructose [1034] Diaz AB, de Souza Moretti MM, Bezerra-Bussoli C, Nunes CCC, Blandinoa A,
catalyzed by hydrochloric acid in subcritical water: formation of da Silva R, et al. Evaluation of microwave-assisted pretreatment of
192 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

lignocellulosic biomass immersed in alkaline glycerol for fermentable sugars [1066] Amarasekara AS, Williams LTD, Ebede CC. Mechanism of the dehydration of
production. Bioresour Technol 2015;185:31623. D-fructose to 5-hydroxymethylfurfural in dimethyl sulfoxide at 150 C: an
[1035] Hu Z, Wen Z. Enhancing enzymatic digestibility of switchgrass by microwave- NMR study. Carbohyd Res 2008;343:30214.
assisted alkali pretreatment. Biochem Eng J 2008;38:36978. [1067] Qu Y, Huang C, Song Y, Zhang J, Chen B. Ecient dehydration of glucose to
[1036] Ninomiya K, Kohori A, Tatsumi M, Osawa K, Endo T, Kakuchi R, et al. Ionic 5-hydroxymethylfurfural catalyzed by the ionic liquid, 1-hydroxyethyl-3-
liquid/ultrasound pretreatment and in-situ enzymatic saccharication of methylimidazolium tetrauoroborate. Bioresour Technol 2012;121:4626.
bagasse using biocompatible cholinium ionic liquid. Bioresour Technol [1068] Ren H, Girisuta B, Zhou Y, Liu L. Selective and recyclable depolymerization
2015;176:16974. of cellulose to levulinic acid catalyzed by acidic ionic liquid. Carbohyd Polym
[1037] Nkemka VN, Murto M. Biogas production from wheat straw in batch and 2015;117:56976.
UASB reactors: the roles of pretreatment and seaweed hydrolysate as a [1069] Saravanamurugan S, Nguyen Van Buu O, Riisager A. Conversion of mono-
co-substrate. Bioresour Technol 2013;128:16472. and disaccharides to ethyl levulinate and ethyl pyranoside with sulfonic
[1038] Zheng Y, Zhao J, Xu F, Li Y. Pretreatment of lignocellulosic biomass for acid-functionalized ionic liquids. ChemSusChem 2011;4:7236.
enhanced biogas production. Prog Energy Combust Sci 2014;42:3553. [1070] Wang G, Zhang Z, Song L. Ecient and selective alcoholysis of furfuryl alcohol
[1039] Beck S, Bouchard J, Berry R. Dispersibility in water of dried nanocrystalline to alkyl levulinates catalyzed by double SO3H-functionalized ionic liquids.
cellulose. Biomacromolecules 2012;13:148694. Green Chem 2014;16:143643.
[1040] Wang Q, Liu S, Yang G, Chen J. Thermogravimetric kinetics of sugarcane [1071] Potvin J, Sorlien E, Hegner J, DeBoef B, Lucht BL. Effect of NaCl on the
bagasse pretreated by hot-water. Bioresour Technol 2013;129:6769. conversion of cellulose to glucose and levulinic acid via solid supported acid
[1041] Pu Y, Jiang N, Ragauskas AJ. Ionic liquid as a green solvent for lignin. J Wood catalysis. Tetrahedron Lett 2011;52:58913.
Chem Technol 2007;27:2333. [1072] Ren H, Zhou Y, Liu L. Selective conversion of cellulose to levulinic acid
[1042] Pinkowska H, Wolak P, Zocinska A. Hydrothermal decomposition of alkali via microwave-assisted synthesis in ionic liquids. Bioresour Technol
lignin in sub- and supercritical water. Chem Eng J 2012;187:41014. 2013;129:61619.
[1043] Azadi P, Farnood R. Review of heterogeneous catalysts for sub- and [1073] Lai L, Zhang Y. The production of 5-hydroxymethylfurfural from fructose in
supercritical water gasication of biomass and wastes. Int J Hydrogen Energy isopropyl alcohol: a green and ecient system. ChemSusChem 2011;4:1745
2011;36:952941. 8.
[1044] Bicker M, Kaiser D, Ott L, Vogel H. Dehydration of D-fructose to [1074] Saha B, Abu-Omar MM. Advances in 5-hydroxymethylfurfural production
hydroxymethylfurfural in sub- and supercritical uids. J Supercrit Fluid from biomass in biphasic solvents. Green Chem 2014;16:2438.
2005;36:11826. [1075] Cai CM, Nagane N, Kumar R, Wyman CE. Coupling metal halides with a
[1045] Fang Z, Xu C. Near-critical and supercritical water and their applications for co-solvent to produce furfural and 5-HMF at high yields directly from
bioreneries. Heidelberg Berlin: Springer-Verlag; 2014. lignocellulosic biomass as an integrated biofuels strategy. Green Chem
[1046] Song J, Fan H, Ma J, Han B. Conversion of glucose and cellulose into value- 2014;16:381929.
added products in water and ionic liquids. Green Chem 2013;15:261935. [1076] Mellmer MA, Gallo JMR, Alonso DM, Dumesic JA. Selective production of
[1047] Pinkert A, Goeke DF, Marsh KN, Pang S. Extracting wood lignin without levulinic acid from furfuryl alcohol in THF solvent systems over H-ZSM-5.
dissolving or degrading cellulose: investigations on the use of food additive- ACS Catal 2015;5:33549.
derived ionic liquids. Green Chem 2011;13:312436. [1077] Weingarten R, Rodriguez-Beuerman A, Cao F, Luterbacher JS, Alonso DM,
[1048] George A, Tran K, Morgan TJ, Benke PI, Berrueco C, Lorente E, et al. The effect Dumesic JA, et al. Selective conversion of cellulose to hydroxymethylfurfural
of ionic liquid cation and anion combinations on the macromolecular in polar aprotic solvents. ChemCatChem 2014;6:222934.
structure of lignins. Green Chem 2011;13:337585. [1078] Cai CM, Zhang T, Kumar R, Wyman CE. THF co-solvent enhances hydrocarbon
[1049] Fang Z, Smith RL, Qi X. Production of biofuels and chemicals with ionic liquids. fuel precursor yields from lignocellulosic biomass. Green Chem
Heidelberg Berlin: Springer-Verlag; 2014. 2013;15:31405.
[1050] Zhang ZC. Catalytic transformation of carbohydrates and lignin in ionic liquids. [1079] Yang Y, Hu CW, Abu-Omar MM. Conversion of carbohydrates and
WIREs Energy Environ 2013;2:65572. lignocellulosic biomass into 5-hydroxymethylfurfural using AlCl36H2O
[1051] Pinkert A, Marsh KN, Pang S, Staiger MP. Ionic liquids and their interaction catalyst in a biphasic solvent system. Green Chem 2012;14:50913.
with cellulose. Chem Rev 2009;109:671228. [1080] Yang Y, Hu CW, Abu-Omar MM. Synthesis of furfural from xylose, xylan, and
[1052] Marcotullio G, Jong WD. Chloride ions enhance furfural formation from biomass using AlCl36H2O in biphasic media via xylose isomerization to
D-xylose in dilute aqueous acidic solutions. Green Chem 2010;12:173946. xylulose. ChemSusChem 2012;5:40510.
[1053] Dutta S, De S, Alam MI, Abu-Omar MM, Saha B. Direct conversion of cellulose [1081] Shen Y, Sun J, Yi Y, Li M, Wang B, Xu F, et al. InCl3-catalyzed conversion of
and lignocellulosic biomass into chemicals and biofuel with metal chloride carbohydrates into 5-hydroxymethylfurfural in biphasic system. Bioresour
catalysts. J Catal 2012;288:815. Technol 2014;172:45760.
[1054] Hsu WH, Lee YY, Peng WH, Wu KCW. Cellulosic conversion in ionic liquids [1082] Pholjaroen B, Li N, Wang Z, Wang A, Zhang T. Dehydration of xylose to furfural
(ILs): effects of H2O/cellulose molar ratios, temperatures, times, and different over niobium phosphate catalyst in biphasic solvent system. J Energy Chem
ILs on the production of monosaccharides and 5-hydroxymethylfurfural 2013;22:82632.
(HMF). Catal Today 2011;174:659. [1083] Ordomsky VV, van der Schaaf J, Schouten JC, Nijhuis TA. Fructose dehydration
[1055] Brandt A, Ray MJ, To TQ, Leak DJ, Murphy RJ, Welton T. Ionic liquid to 5-hydroxymethylfurfural over solid acid catalysts in a biphasic system.
pretreatment of lignocellulosic biomass with ionic liquidwater mixtures. ChemSusChem 2012;5:181219.
Green Chem 2011;13:248999. [1084] Romn-Leshkov Y, Chheda JN, Dumesic JA. Phase modiers promote ecient
[1056] Qi X, Watanabe M, Aida TM, Smith RL. Synergistic conversion of glucose into production of hydroxymethylfurfural from fructose. Science 2006;312:1933
5-hydroxymethylfurfural in ionic liquidwater mixtures. Bioresour Technol 7.
2012;109:2248. [1085] Ordomsky VV, van der Schaaf J, Schouten JC, Nijhuis TA. The effect of solvent
[1057] Govinda V, Attri P, Venkatesu P, Venkateswarlu P. Thermophysical properties addition on fructose dehydration to 5-hydroxymethylfurfural in biphasic
of dimethylsulfoxide with ionic liquids at various temperatures. Fluid Phase system over zeolites. J Catal 2012;287:6875.
Equilib 2011;304:3543. [1086] Okano T, Qiao K, Bao Q, Tomida D, Hagiwara H, Yokoyama C. Dehydration
[1058] Xiao S, Liu B, Wang Y, Fang Z, Zhang Z. Ecient conversion of cellulose into of fructose to 5-hydroxymethylfurfural (HMF) in an aqueous acetonitrile
biofuel precursor 5-hydroxymethylfurfural in dimethyl sulfoxideionic liquid biphasic system in the presence of acidic ionic liquids. Appl Catal A Gen
mixtures. Bioresour Technol 2014;151:3616. 2013;451:15.
[1059] Zhang Z, Liu B, Zhao Z. Conversion of fructose into 5-HMF catalyzed by GeCl4 [1087] Romn-Leshkov Y, Dumesic JA. Solvent effects on fructose dehydration to
in DMSO and [Bmim]Cl system at room temperature. Carbohyd Polym 5-hydroxymethylfurfural in biphasic systems saturated with inorganic salts.
2012;88:8915. Top Catal 2009;52:297303.
[1060] Mushrif SH, Caratzoulas S, Vlachos DG. Understanding solvent effects in the [1088] Wang W, Ren J, Li H, Deng A, Sun R. Direct transformation of xylan-type
selective conversion of fructose to 5-hydroxymethyl-furfural: a molecular hemicelluloses to furfural via SnCl4 catalysts in aqueous and biphasic systems.
dynamics investigation. Phys Chem Chem Phys 2012;14:263744. Bioresour Technol 2015;183:18894.
[1061] Tsilomelekis G, Josephson TR, Nikolakis V, Caratzoulas S. Origin of [1089] Alonso DM, Wettstein SG, Bond JQ, Root TW, Dumesic JA. Production of
5-hydroxymethylfurfural stability in water/dimethyl sulfoxide mixtures. biofuels from cellulose and corn stover using alkylphenol solvents.
ChemSusChem 2014;7:11726. ChemSusChem 2011;4:107881.
[1062] Wang H, Deng T, Wang Y, Qi Y, Hou X, Zhu Y. Ecient catalytic system for [1090] Mellmer MA, Sener C, Gallo JMR, Luterbacher JS, Alonso DM, Dumesic JA.
the conversion of fructose into 5-ethoxymethylfurfural. Bioresour Technol Solvent effects in acid-catalyzed biomass conversion reactions. Angew Chem
2013;136:394400. Int Ed 2014;53:118725.
[1063] Beckerle K, Okuda J. Conversion of glucose and cellobiose into [1091] Mellmer MA, Alonso DM, Luterbacher JS, Gallo JMR, Dumesic JA. Effects of
5-hydroxymethylfurfural (HMF) by rare earth metal salts in N,N- -valerolactone in hydrolysis of lignocellulosic biomass to monosaccharides.
dimethylacetamide (DMA). J Mol Catal A Chem 2012;356:15864. Green Chem 2014;16:465962.
[1064] Vasudevan V, Mushrif SH. Insights into the solvation of glucose in [1092] Zhang L, Yu H, Wang P, Li Y. Production of furfural from xylose, xylan and
water, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF) and N,N- corncob in gamma-valerolactone using FeCl36H2O as catalyst. Bioresour
dimethylformamide (DMF) and its possible implications on the conversion Technol 2014;151:35560.
of glucose to platform chemicals. RSC Adv 2015;5:2075663. [1093] Qi L, Yiu Mui F, Lo SW, Lui M, Akien GR, Horvth IT. Catalytic conversion of
[1065] Yang Y, Liu W, Wang N, Wang H, Song Z, Li W. Effect of organic solvent and fructose, glucose, and sucrose to 5-(hydroxymethyl)furfural and levulinic and
Bronsted acid on 5-hydroxymethylfurfural preparation from glucose over formic acids in -valerolactone as a green solvent. ACS Catal 2014;4:1470
CrCl3. RSC Adv 2015;5:2780513. 7.
H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194 193

[1094] Cui J, Tan J, Deng T, Cui X, Zheng H, Zhu Y, et al. Direct conversion of [1127] Budarin VL, Shuttleworth PS, De bruyn MD, Farmer TJ, Gronnow MJ, Pfaltzgraff
carbohydrates to -valerolactone facilitated by solvent effect. Green Chem L, et al. The potential of microwave technology for the recovery, synthesisand
2015;17:30849. manufacturing of chemicals from bio-wastes. Catal Today 2015;239:80
[1095] Caretto A, Perosa A. Upgrading of levulinic acid with dimethylcarbonate as 9.
solvent/reagent. ACS Sust Chem Eng 2013;1:98994. [1128] Xie Q, Borges FC, Cheng Y, Wan Y, Li Y, Lin X, et al. Fast microwave-assisted
[1096] Gao W, Li Y, Xiang Z, Chen K, Yang R, Argyropoulos DS. Ecient one-pot catalytic gasication of biomass for syngas production and tar removal.
synthesis of 5-chloromethylfurfural (CMF) from carbohydrates in mild Bioresour Technol 2014;156:2916.
biphasic systems. Molecules 2013;18:767585. [1129] Salema AA, Ani FN. Microwave induced pyrolysis of oil palm biomass.
[1097] Kumari N, Olesen JK, Pedersen CM, Bols M. Synthesis of 5- Bioresour Technol 2011;102:338895.
bromomethylfurfural from cellulose as a potential intermediate for biofuel. [1130] Bu Q, Lei H, Ren S, Wang L, Zhang Q, Tang J, et al. Production of phenols and
Eur J Org Chem 2011;2011:126670. biofuels by catalytic microwave pyrolysis of lignocellulosic biomass. Bioresour
[1098] Zhang J, Wu R, Zhang G, Yao C, Zhang Y, Wang Y, et al. Recent studies on Technol 2012;108:2749.
chemical engineering fundamentals for fuel pyrolysis and gasication in dual [1131] Mushtaq F, Mat R, Ani FN. A review on microwave assisted pyrolysis of coal
uidized bed. Ind Eng Chem Res 2013;52:6283302. and biomass for fuel production. Renew Sust Energy Rev 2014;39:55574.
[1099] Luo J, Fang Z, Smith RL. Ultrasound-enhanced conversion of biomass to [1132] Richel A, Laurent P, Wathelet B, Wathelet JP, Paquot M. Microwave-assisted
biofuels. Prog Energy Combust Sci 2014;41:5693. conversion of carbohydrates. State of the art and outlook. C R Chimie
[1100] Rinaldi R, Schth F. Design of solid catalysts for the conversion of biomass. 2011;14:22434.
Energy Environ Sci 2009;2:61026. [1133] Zhang Z, Zhao ZK. Solid acid and microwave-assisted hydrolysis of cellulose
[1101] Mittelbach M, Schober S. The inuence of antioxidants on the oxidation in ionic liquid. Carbohyd Res 2009;344:206972.
stability of biodiesel. J Am Oil Chem Soc 2003;80:81723. [1134] Szabolcs , Molnr M, Dib G, Mika LT. Microwave-assisted conversion of
[1102] Tanabe K, Misono M, Ono Y, Hattori H. New solid acids and bases: their carbohydrates to levulinic acid: an essential step in biomass conversion. Green
catalytic properties. Amsterdam: Elsevier; 1989. Chem 2013;15:43945.
[1103] Bruggink A, Schoevaart R, Kieboom T. Concepts of nature in organic synthesis: [1135] Zhang Z, Zhao ZK. Microwave-assisted conversion of lignocellulosic biomass
cascade catalysis and multistep conversions in concert. Org Process Res Dev into furans in ionic liquid. Bioresour Technol 2010;101:111114.
2003;7:62240. [1136] Qi X, Watanabe M, Aida TM, Smith RL. Fast transformation of glucose and
[1104] Csicsery SM. Shape-selective catalysis in zeolites. Zeolites 1984;4:202 di-/polysaccharides into 5-hydroxymethylfurfural by microwave heating in
13. an ionic liquid/catalyst system. ChemSusChem 2010;3:10717.
[1105] Taguchi A, Schth F. Ordered mesoporous materials in catalysis. Micropor [1137] Yemis O, Mazza G. Acid-catalyzed conversion of xylose, xylan and straw into
Mesopor Mat 2005;77:145. furfural by microwave-assisted reaction. Bioresour Technol 2011;102:7371
[1106] Schth F, Schmidt W. Microporous and mesoporous materials. Adv Mater 8.
2002;14:62938. [1138] Koberg M, Cohen M, Ben-Amotz A, Gedanken A. Bio-diesel production directly
[1107] Wan Y, Yang HF, Zhao DY. Hostguest chemistry in the synthesis of ordered from the microalgae biomass of Nannochloropsis by microwave and
nonsiliceous mesoporous materials. Acc Chem Res 2006;39:42332. ultrasound radiation. Bioresour Technol 2011;102:42659.
[1108] Harada T, Ikeda S, Ng YH, Sakata T, Mori H, Torimoto T, et al. Rhodium [1139] Patil PD, Gude VG, Mannarswamy A, Cooke P, Nirmalakhandan N, Lammers
nanoparticle encapsulated in a porous carbon shell as an active heterogeneous P, et al. Comparison of direct transesterication of algal biomass under
catalyst for aromatic hydrogenation. Adv Funct Mater 2008;18:2190 supercritical methanol and microwave irradiation conditions. Fuel
6. 2012;97:82231.
[1109] Guo F, Fang Z, Zhou T-J. Conversion of fructose and glucose into [1140] Rocha MVP, de Matos LJBL, de Lima LP, da Silva Figueiredo PM, Lucena IL,
5-hydroxymethylfurfural with lignin-derived carbonaceous catalyst under Fernandes FAN, et al. Ultrasound-assisted production of biodiesel and ethanol
microwave irradiation in dimethyl sulfoxideionic liquid mixtures. Bioresour from spent coffee grounds. Bioresour Technol 2014;167:3438.
Technol 2012;112:31318. [1141] Veljkovic VB, Avramovic JM, Stamenkovic OS. Biodiesel production by
[1110] Kubicka D, Kikhtyanin O. Opportunities for zeolites in biomass upgrading ultrasound-assisted transesterication: state of the art and the perspectives.
Lessons from the rening and petrochemical industry. Catal Today Renew Sust Energy Rev 2012;16:1193209.
2015;243:1022. [1142] Zhang F, Fang Z, Wang YT. Biodiesel production directly from oils with high
[1111] Zi G, Yan Z, Wang Y, Chen Y, Guo Y, Yuan F, et al. Catalytic hydrothermal acid value by magnetic Na2SiO3@Fe3O4/C catalyst and ultrasound. Fuel
conversion of carboxymethyl cellulose to value-added chemicals over 2015;150:3707.
metalorganic framework MIL-53(Al). Carbohyd Polym 2015;115:146 [1143] Subhedar PB, Gogate PR. Intensication of enzymatic hydrolysis of
51. lignocellulose using ultrasound for ecient bioethanol production: a review.
[1112] Chen J, Liu R, Guo Y, Chen L, Gao H. Selective hydrogenation of biomass-based Ind Eng Chem Res 2013;52:1181628.
5-hydroxymethylfurfural over catalyst of palladium immobilized on amine- [1144] Karimi M, Jenkins B, Stroeve P. Ultrasound irradiation in the production of
functionalized metalorganic frameworks. ACS Catal 2015;5:72233. ethanol from biomass. Renew Sust Energy Rev 2014;40:40021.
[1113] Chen J, Li K, Chen L, Liu R, Huang X, Ye D. Conversion of fructose into
5-hydroxymethylfurfural catalyzed by recyclable sulfonic acid-functionalized
metalorganic frameworks. Green Chem 2014;16:24909. Hu Li is a postdoctoral fellow of Agricultural Engi-
[1114] Schth F, Sing KSW, Weitkamp J. Handbook of porous materials. Weinheim: neering under supervision of Professor Zhen Fang,
Wiley-VCH; 2002. Nanjing Agricultural University, China. Dr. Li ob-
[1115] Ogihara Y, Smith RL, Inomata H, Ara K. Direct observation of cellulose tained his PhD [Co-supervisors: Professor Song Yang,
dissolution in subcritical and supercritical water over a wide range of water Professor Zhen Fang (Chinese Academy of Sciences)
densities (5501000 kg/m3). Cellulose 2005;12:595606. and Associate Professor Anders Riisager (Technical
[1116] Okuhara T. Water-tolerant solid acid catalysts. Chem Rev 2002;102:3641 University of Denmark)] from Center for R&D of Fine
66. Chemicals, Guizhou University, China. His research
[1117] Lai DM, Deng L, Guo QX, Fu Y. Hydrolysis of biomass by magnetic solid acid. focuses on the catalytic conversion of biomass into
Energy Environ Sci 2011;4:35527. chemicals and biofuels with functional catalytic ma-
[1118] Gawande MB, Branco PS, Varma RS. Nano-magnetite (Fe3O4) as a support terials. Dr. Li has co-authored more than 30 peer-
for recyclable catalysts in the development of sustainable methodologies. reviewed papers on biomass valorization. He is a guest
Chem Soc Rev 2013;42:337193. editor of Current Organic Chemistry and an editori-
[1119] Shuttleworth PS, De bruyn M, Parker HL, Hunt AJ, Budarin VL, Matharu AS, al board member of Frontiers in Applied Chemistry.
et al. Applications of nanoparticles in biomass conversion to chemicals and
fuels. Green Chem 2014;16:57384.
[1120] Luque R, Menndez JA, Arenillas A, Cot J. Microwave-assisted pyrolysis of
biomass feedstocks: the way forward? Energy Environ Sci 2012;5:5481
8. Zhen Fang is professor and leader of biomass group,
[1121] Moseley JD, Kappe CO. A critical assessment of the greenness and energy Nanjing Agricultural University. He is the inventor of
eciency of microwave-assisted organic synthesis. Green Chem the fast hydrolysis process. He is listed in the Most
2011;13:794806. Cited Chinese Researchers in energy for 2014 and
[1122] Yin C. Microwave-assisted pyrolysis of biomass for liquid biofuels production. 2015 (Elsevier-Scopus). Professor Fang specializes in
Bioresour Technol 2012;120:27384. thermal/biochemical conversion of biomass,
[1123] Chen WH, Tu YJ, Sheen HK. Disruption of sugarcane bagasse lignocellulosic nanocatalyst synthesis and its applications, and pre-
structure by means of dilute sulfuric acid pretreatment with microwave treatment of biomass for bioreneries. He obtained
assisted heating. Appl Energ 2011;88:272634. his PhDs from China Agricultural University (Biolog-
[1124] Lan W, Liu CF, Yue FX. Ultrasound-assisted dissolution of cellulose in ionic ical and Agricultural Engineering, Beijing) and McGill
liquid. Carbohyd Polym 2011;86:6727. University (Materials Engineering, Montreal).
[1125] Fang Z, Smith RL, Qi X. Production of biofuels and chemicals with microwave. Professor Fang is Editor-in-Chief, Springer Book Series
Heidelberg Berlin: Springer-Verlag; 2015. - Biofuels and Bioreneries; associate editor of Bio-
[1126] Fang Z, Smith RL, Qi X. Production of biofuels and chemicals with ultrasound. technology for Biofuels, and is serving on editorial
Heidelberg Berlin: Springer-Verlag; 2015. boards of major international journals in energy.
194 H. Li et al. / Progress in Energy and Combustion Science 55 (2016) 98194

Richard L. Smith, Jr. is professor of Chemical Engineer- Song Yang is professor and director of Center for R&D
ing, Graduate School of Environmental Studies, Research of Fine Chemicals, Guizhou University, China. Pro-
Center of Supercritical Fluid Technology, Tohoku Uni- fessor Yang obtained his PhD from Guizhou University
versity, Japan. Professor Smith has a strong background (with Professor Baoan Song). He accepted a post-
in physical properties and separations and obtained his doctoral position in the University of Texas
PhD in chemical engineering from the Georgia Insti- Southwestern Medical Center at Dallas, USA. His re-
tute of Technology (USA). His research focuses on search interests include the rational design of
developing green chemical processes especially those heterogeneous catalysts for biomass conversions, and
that use water and carbon dioxide as the solvents in their the discovery of new antiviral agents. Professor Yang
supercritical state. He has expertise in physical proper- is an associate editor of RSC Advances and editorial
ty measurements and in separation techniques with board members of Current Nanoscience and Current
ionic liquids and published has more than 200 scien- Catalysis. He was appointed as Distinguished Profes-
tic papers, patents, and reports in the eld of chemical sor of Cheung Kong Scholars Program in 2013, and
engineering. Professor Smith is the Asia regional editor has authored 12 patents and more than 100 scien-
for the Journal of Supercritical Fluids and has served on tic papers in international journals.
editorial boards of major international journals associ-
ated with properties and energy.